Maria Csuros

Environmental
Sampling and
Analysis
for Metals
L1572 Front Matter 5/24/02 10:49 AM Page ii
Environmental
Sampling and
Analysis
for Metals
Maria Csuros • Csaba Csuros
With contributions by
Laszlo Gy. Szabo
LEWIS PUBLISHERS
A CRC Press Company
Boca Raton London New York Washington, D.C.
L1572 Front Matter 5/24/02 10:49 AM Page iv
Library of Congress Cataloging-in-Publication Data

Csuros, Maria.
Environmental sampling and analysis for metals / by Maria Csuros and Csaba Csuros.
p. cm.
Includes bibliographical references and index.
ISBN 1-56670-572-X (alk. paper)
1. Metals—Analysis. 2. Environmental chemistry. 3. Environmental monitoring I.
Csuros, Csaba II. Title.
TD196.M4 C78 2002

628.5′2—dc21 2002019440
CIP
This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with per-
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Printed on acid-free paper
L1572 Front Matter 5/24/02 10:49 AM Page v
To all who are so far from us, but always close to our hearts,
our sons Geza and Zoltan, and our grandchildren Aaron,
Andrew, Daniel, Jordan, and Sebastian.
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Preface
Monitoring the environment for metals has become a topic of considerable importance, not only to
those industries emitting heavy metals but also to surveillance agencies and other organizations as-
sessing the impact of metals on the environment. Our goal is to provide a comprehensive and easy-
to-read text for anyone working in the environmental analytical chemistry arena and to provide
essential information to consultants and regulators about analytical and quality control procedures
helpful in their evaluation and decision-making procedures. The book is also useful for technicians
in their everyday chores. It not only provides a guide for analyzing metals in environmental samples
but is useful as a supplementary information source for more general environmental studies and a
variety of job-related training programs. In addition, college and university students taking chemi-
cal or environmental laboratory courses will find the book easy to use and understand. It will also be
helpful to graduate students and chemists seeking information on laboratory practice.
The book provides a detailed introduction to metals and their toxicity and includes sample col-
lection, preservation, correct storage, holding time, preparation for analysis, theory of analytical
methods and instrumentation, step-by-step analytical procedures, complete QA/QC requirements,
data validation, calculation of analytical results, reporting format, and standards with maximum con-
taminant levels. The book contains both theoretical and practical applications in metals analysis of
environmental samples and incorporates the latest in analytical techniques, instrumentation, and reg-
ulations. The appendices provide instant information on a wide array of topics.
This book is part of the “Environmental Sampling and Analysis for Laboratory Technicians” se-
ries, and should prove valuable as a practical handbook for students in environmental education and
special training programs and for environmental chemists in everyday chores. In addition, the text
will help students, chemists, and others understand analytical reports.
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Acknowledgments
We owe a great debt and gratitude to all the people who participated in making this book possible.
We are honored to thank Attila Borhidy, head of the Hungarian Academy of Science. He has been
responsible for the development of our scientific relationships with the outstanding staff of the
University of Pecs, Hungary. Special thanks to Laszlo Szabo, chair of the Biology Department of the
University of Pecs, for his helpful comments and support. His contribution to this text has made this
book more valuable.
We are pleased to express our gratitude to our son Geza and his wife for their patience in re-
viewing and correcting the text. Our appreciation goes also to Sandor Barta for proofreading and im-
proving the writing; Lenke Babarci for her patience and hard work in the preparation of the figures
and tables; and Barna Csuros, retired library director, for the literature he sent for our review and for
his always available helping hand.
We also gratefully acknowledge the support of the outstanding editorial and production staff of
CRC Press/Lewis Publishers.
Warm words of thanks to our sons, Geza and Zoltan, and our grandchildren, Aaron, Andrew,
Daniel, Jordan, and Sebastian, for their love, encouragement, and cheerful spirit.
To all of you, thank you!
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Biographies
Maria Csuros is an environmental research chemist, currently affiliated with the University of Pecs,
Hungary. She previously worked as supervisor of the water department for the Environmental and
Public Health Laboratory, Hungary, and has served in diverse teaching and research capacities in the
United States. Ms. Csuros designed and developed an environmental science program with a focus
on sampling and analysis for the Pensacola Junior College, Florida. She received her Ph.D. in envi-
ronmental chemistry from the Janus Pannonius University, Pecs, Hungary. In addition to this book,
Ms. Csuros has authored or co-authored Environmental Sampling and Analysis for Technicians,
1994; Environmental Sampling and Analysis Laboratory Manual, 1996; and Microbiological
Examination of Water and Wastewater, 1999, all published by CRC Press/Lewis.
Csaba Csuros teaches advanced microbiology courses and conducts research on the serological di-
agnosis of parasitic diseases (ascariasis, echinococcosis, and filariasis) at the University of Pecs,
Hungary. He previously worked in several capacities in medical and public health testing laborato-
ries, and as a professor of microbiology, anatomy, and physiology in U.S. universities; he has re-
ceived the excellence in teaching award. Mr Csuros earned his Ph.D. in microbiology from the Jozsef
Attila University, Hungary. He has written numerous papers in the field of microbiology and co-au-
thored Microbiological Examination of Water and Wastewater, 1999, CRC Press/Lewis.
Laszlo Gy. Szabo is chair of the Botany Department and teaches graduate-level plant physiology
and ecological phytochemistry at the University of Pecs, Hungary. He received a Ph.D. and D.Sc. in
plant physiology (phytochemistry) from the Hungarian Academy of Science, Budapest, Hungary,
and a M.S. degree in pharmacy from Semmelweis University, also in Budapest. Mr. Szabo has writ-
ten several monographs published by the University of Pecs and Academic Publishers, Budapest. He
is vice president of the Medicinal Plant Section, Hungarian Pharmaceutical Society; a member of the
International Allelopathy Society, Federation of European Societies of Plant Physiology, and the
Botanical Committee of the Hungarian Academy of Sciences; and serves on the editorial board of
The Cultural Flora of Hungary.
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List of Figures and Tables

FIGURES
1.1 Typical atom.

1.2 Block located in the periodic table.
1.3 Electron sea model.
2.1 Sodium-potassium exchange pump.
2.2 Electrochemical process involved in rusting of iron.
2.3 Rust prevention.
2.4 Formula of vitamin B12.
2.5 Hemoglobin structure.
3.1 Ames test for detecting chemical mutagen.
3.2 Carcinogenic aromatic hydrocarbons.
3.3 Glutathione reaction with a metal.
3.4 Structure of chelate formed when the anion of the EDTA envelopes a Pb2+ ion.
3.5 BAL chelation of As or heavy metal ion.
5.1 The nature of waves.
5.2 Electromagnetic radiation.
5.3 Continuous spectrum obtaining all wavelengths of visible light; hydrogen line containing only
a few discrete wavelengths.
5.4 Electronic energy transition.
5.5 Atomic spectroscopy systems.
6.1 Basic construction of a simple spectrophotometer.
6.2 Lining up a cuvette for insertion into the cuvette holder.
6.3. Schematic diagram of a phototube.
6.4 Block diagram showing components of a single-beam spectrophotometer.
6.5 Schematic diagram of a double-beam spectrophotometer.
6.6 Conversion of wavelength and wavenumber.
6.7 Typical calibration curve.
6.8 Documentation of spectrophotometer wavelength calibration check.
6.9 Documentation of spectrophotometer linearity check.
6.10 Performance check of infrared (IR) spectrophotometer.
7.1 Hollow cathode lamp.
7.2 Electrodeless discharge lamp.
7.3 Premix burner system.
7.4 A monochromator.
7.5 Basic AA instrument.
7.6 Standard additions method.
7.7 Continuum source background corrector.
7.8. Zeeman effect.
7.9 Zeeman effect background correction.
7.10 AA instrument showing fume hood and drain line.
9.1 Graphite furnace atomizer.
9.2 L’vov platform.
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10.1 Schematic arrangement of equipment for measurement of mercury by the cold-vapor atomic
absorption technique.
11.1 Manual reaction cell for producing As and Se hydrides.
12.1 ICP zones.
12.2 Temperature regions of typical ICP discharge.
12.3 Major components and layout of a typical ICP-AES instrument.
12.4 Schematic of a torch used for ICP-AES.
12.5 Photocathode, dynode, and anode layout of a photomultiplier tube.
13.1 Documentation log form for purchased calibration stock and standard solutions.
13.2 Documentation log form for preparation of calibration stock solution.
13.3 Documentation log form for preparation of calibration standards.
13.4 Documentation log form for preparation of CVS or QC check standards.
13.5 Interpretation of quality control charts.
14.1 Sample holding-time log.
14.2 Chain-of-custody form.
14.3 Sample label.
14.4 Field notebook.
14.5 Sample field log.
14.6 Preservative preparation log.
14.7 Field sample spike preparation log.
14.8 Teflon bailer.
14.9 Modified Kemmerer sampler.
14.10 Eckman bottom-grab sampler.
14.11 Composite liquid waste sampler, colivasa.
14.12 Sampling trier, used in sticky solids and loose soils.
14.13 Safety labels.
A.1 Diagram of a simple mass spectrophotometer showing separation of neon isotopes.
A.2 Mass spectrophotometer.
B.1 Schematic drawing of silicon semiconductor crystal layers.
C.1 Ruby laser.
E.1 Cyanide poisoning.
F.1 Structure of DNA.
G.1 Polarized light in contrast to ordinary light.
K.1 Soxhlet extraction.
L.1 SI units and conversion factors.
TABLES
1.1 Names and Symbols of Elements Derived from Latin Words

1.2 Origins of Selected Element Names
1.3 Properties of Subatomic Particles
1.4 Table of Elements with Atomic Numbers and Atomic Masses
1.5 Periodic Table of the Elements
1.6 Periodic Table with Names of Chemical Groups
1.7 Metals, Nonmetals, and Metalloids Located on the Periodic Table
1.8 Characteristics of Metals and Nonmetals
2.1 Metals with Multiple Oxidation States
3.1 Selected Corrosive Poisons
3.2 Teratogenic Substances and Effects on Fetuses of Selected Species
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3.3 Selected Inorganic Chemicals Carcinogenic to Humans

3.4 Selected Arsenic-Containing Insecticides
4.1 Drinking Water Standards
4.2 Priority Toxic Pollutants
4.3 Recommended Maximum Concentrations of Trace Elements in Irrigation Water
4.4 Maximum Concentration of Contaminants in Characterization of EP Toxicity
4.5 Toxic Characteristic Leachate Pollutants (TCLPs) and Regulatory Levels
5.1 Wavelength Regions by Color
6.1 Visible Spectrum and Complementary Colors
6.2 Ultraviolet and Visible Radiation Sources
7.1 Atomic Absorption Concentration Ranges
7.2 Maintenance of Atomic Absorption Spectrophotometer
8.1 Atomic Absorption Concentration Ranges, FAAS Technique
8.2 Maintenance of FAAS
8.3 FAAS Performance Check
8.4 Standard Conditions for Flame AAS
9.1 Detection Limits and Concentration Ranges for GrAAS
9.2 Matrix Modifiers Added to Sample to Eliminate Interference, GrAAS Technique
9.3 Maintenance of GrAAS
9.4 Performance Check for GrAAS
12.1 Recommended Wavelengths and Estimated Instrumental Detection Limits for ICP
12.2 Suggested Wavelengths, Estimated Detection Levels, Alternate Wavelengths, Calibration
Concentrations, and Upper Limits
12.3 Analyte Concentration Equivalents Arising from Interference at the 100-mg/l Level
13.1 Quality Check of Laboratory-Pure Water
13.2 Documentation of Laboratory-Pure Water Quality
13.3 Student’s t Table
13.4 Monitoring Form for Precision (RPD) Values
13.5 Monitoring Form for Accuracy (% Recovery) Values
13.6 Monitoring Form for Spike Recovery (%Rsp) Values
15.1 Acids Used in Conjunction with HNO3 for Sample Preparation
15.2 Suggested Sample Volumes for Digestion
15.3 Sample Preparation Log Sheet (per Analyte Group)
15.4 Disposal Log Form for Digestates and Extracts
16.1 Two-Way Conversion Factors for mg/l to meq/l and Vice Versa
16.2 Working Paper for Spectrophotometric Analysis (Water Samples)
16.3 Working Paper for Spectrophotometric Analysis (Solid Samples)
16.4 Working Paper for Atomic Absorption Spectroscopy
16.5 Noncompliance Report Form
18.1 Methods for Determination of Metals
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Table of Contents
Chapter 1 Introduction to Metals

1.1 Introduction to Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1
1.1.1 Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..1
1.1.2 Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1
1.1.3 Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2
1.1.4 Isotopes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..4
1.2 Periodic Table of Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4
1.3 Properties of Metals, Nonmetals, and Metalloids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
1.3.1 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
1.3.2 Nonmetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
1.3.3 Metalloids or Semimetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10
1.4 Early History of Metal Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..11
1.5 Sources of Metals and Their Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11
1.6 Sources of Metal Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11
1.6.1 Metal Pollution from Mining and Processing Ores . . . . . . . . . . . . . . . . . . . . . . . . . .11
1.6.2 Other Sources of Metal Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12
Chapter 2 Discussion of Metallic Elements

2.1 Representative Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13
2.1.1 Group IA (1): Alkali Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13
2.1.2 Group IIA (2): Alkaline Earth Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15
2.1.3 Group IIIA (13) Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18
2.1.4 Group IVA (14) Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .19
2.1.5 Group VA (15) Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..20
2.2 Transition Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .20
2.2.1 General Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .20
2.2.2 Inner Transition Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .30
2.3 Metalloids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .31
2.3.1 Group IVA (14) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .31
2.3.2 Group VA (15) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .31
2.4 Heavy Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .31
2.5 Metallic Substances Essential to Life . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .32
2.5.1 Most Important Metals in Human Metabolism . . . . . . . . . . . . . . . . . . . . . . . . . . . . .32
2.5.2 Common Plant Nutrients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .37
Chapter 3 Toxicity of Metals

3.1 General Discussion of Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
3.1.1 Toxicytosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
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3.1.2 Toxic Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..39

3.1.3 Acute Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
3.1.4 Chronic Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
3.1.5 Lethal Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
3.1.6 Sublethal Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
3.1.7 TWO D’S (Dose and Duration) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .40
3.1.8 LD50 (Lethal Dose 50) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .40
3.1.9 Classification of Toxic Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .40
3.2 Metal Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .44
3.3 Toxic Effects of Selected Representative Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .46
3.3.1 Group IA (1): Alkali Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .46
3.3.2 Group IIA (2): Alkaline Earth Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .47
3.3.3 Group IIIA (13): Boron–Aluminum (B–Al) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .47
3.3.4 Group IVA (14): Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .49
3.3.5 Group VA (15): Nitrogen–Phosphorus (N–P) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .50
3.4 Toxicity of Selected Transition Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .50
3.4.1 Period 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .50
3.4.2 Period 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .51
3.4.3 Period 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .53
3.4.4 Selected Metals of Period 7, Including Actinides . . . . . . . . . . . . . . . . . . . . . . . . . . .55
3.5 Toxicity of Selected Metalloids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .55
3.5.1 Boron (B) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .55
3.5.2 Germanium (Ge) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .56
3.5.3 Arsenic (As) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .56
3.5.4 Antimony (Sb) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .57
3.5.5 Tellurium (Te) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .57
Chapter 4 STANDARDS RELATED TO METALLIC POLLUTANTS

4.1 Environmental Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .59
4.1.1 Federal and State Environmental Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .59
4.1.2 Environmental Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .60
4.1.3 Selected Regulatory Programs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .60
4.2 Drinking Water Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .61
4.2.1 Safe Drinking Water Act (SDWA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .61
4.2.2 SDWA Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .62
4.2.3 SDWA Amendments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .62
4.2.4 National Secondary Drinking Water Regulations (NSDWRs) . . . . . . . . . . . . . . . . .67
4.3 Surfacewater Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .67
4.3.1 Clean Water Act (CWA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .68
4.3.2 EPA Priority Toxic Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .69
4.4 Agriculturally Used Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .69
4.5 Industrial Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .71
4.6 Waste Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .72
4.7 Hazardous Waste Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .73
4.7.1 Criteria for Hazardous Waste Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .73
4.8 Air Pollution and Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .74
4.8.1 Primary and Secondary Air Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .74
4.8.2 Clean Air Act (CAA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .74
4.8.3 Ambient Air Quality Standard (AAQS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .76
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4.9 ISO 14001 and Environmental Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .77

4.9.1 Environmental Management Systems (EMSs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . .77
4.9.2 ISO 14001 EMS Standard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .77
Chapter 5 FUNDAMENTALS OF SPECTROSCOPY

5.1 Early History of the Nature of Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .79
5.2 Electromagnetic Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .80
5.2.1 The Dual Nature of Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .81
5.3 Continuous and Line Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .82
5.3.1 Continuous Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .82
5.3.2 Line Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .83
5.4 Absorption and Emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .83
5.4.1 Molecular vs. Atomic Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .84
5.5 Beer’s Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .85
5.6 Atomic Spectroscopy Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .86
5.6.1 Atomic Absorption Spectrometry (AAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .86
5.6.2 Atomic Emission Spectrometry (AES) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .86
5.6.3 Atomic Fluorescence Spectrometry (AFS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .87
5.6.4 Atomization Process and Excitation Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .87
5 6.5 Development of Analytical Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .87
5.6.6 Comparison of Techniques Used in Trace Element Analysis . . . . . . . . . . . . . . . . . .88
Chapter 6 MOLECULAR SPECTROPHOTOMETRY

6.1 Molecular Absorption and Color . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .89
6.2 Molecular Absorption Spectrophotometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .89
6.2.1 Basic Components of Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .89
6.3 Single-Beam and Double-Beam Spectrophotometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .93
6.3.1 Single-Beam Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .93
6.3.2 Double-Beam Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .93
6.4 Type of Spectrophotometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .94
6.4.1 Visible Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .94
6.4.2 Ultraviolet/Visible (UV/Vis) Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . .94
6.4.3 Spectrophotometers with a Built-in Microprocessor or Microcomputer . . . . . . . . . .95
6.4.4 Differences between UV/Vis and IR Spectrophotometric Methods . . . . . . . . . . . . .95
6.4.5 Infrared (IR) Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .95
6.5 Summary of Molecular Spectrophotometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .97
6.6 Spectrophotometer Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .97
6.6.1 Frequency of Calibration Curve Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .97
6.6.2 General Rules in the Preparation of Calibration Curves . . . . . . . . . . . . . . . . . . . . . .98
6.6.3 Linear Regression Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .98
6.7 Performance Check of UV/Vis and IR Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . .100
6.7.1 UV/Vis Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .100
6.7.2 IR Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .101
6.8 Maintenance of the UV/Vis and IR Spectrophotometers . . . . . . . . . . . . . . . . . . . . . . . . . .101
6.8.1 UV/Vis Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .101
6.8.2 IR Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .101
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Chapter 7 ATOMIC ABSORPTION SPECTROMETRY

7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .103
7.1.1 Atomic Spectrometry (AS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .103
7.1.2 Atomic Absorption (AA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .103
7.1.3 Atomic Absorption Spectrometry (AAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .103
7.2 Steps in the Atomic Absorption Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104
7.2.1 Nebulization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104
7.2.2 Evaporation or Desolvation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104
7.2.3 Liquefaction and Vaporization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104
7.2.4 Atomization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .105
7.2.5 Excitation and Ionization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .105
7.3 Atomic Absorption Spectrophotometer Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . .105
7.3.1 Light Source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .105
7.3.2 Flames . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .106
7.3.3 Nebulizer and Burner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .106
7.3.4 Optics and Monochromator System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .107
7.3.5 Detector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .108
7.3.6 Readout System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .108
7.3.7 Automatic Samplers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
7.3.8 Automated Multielement AA Instruments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
7.3.9 Microcomputer-Based Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
7.4 Single- and Double-Beam Instruments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
7.5 Atomic Absorption Measurement Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
7.5.1 Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
7.5.2 Concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .110
7.5.3 Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .110
7.5.4 Detection Limit (DL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .110
7.5.5 Optimum Concentration Ranges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .110
7.6 Techniques in AAS Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .112
7.6.1 Direct-Aspiration or Flame Atomic Absorption Spectrophotometry (FAAS) . . . . .112
7.6.2 Chelation-Extraction Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .112
7.6.3 Hydride Generation Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .112
7.6.4 Cold Vapor Atomic Absorption Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . .113
7.6.5 Electrothermal or Graphite Furnace Atomic Absorption
Spectrophotometry (GrAAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .113
7.7 Interference in AAS Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .113
7.7.1 Nonspectral Interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .113
7.7.2 Spectral Interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .116
7.7.3 Summary of Interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .117
7.8 Safety in AAS Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .118
7.8.1 Flammability of Acetylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .118
7.8.2 Combustion Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .118
7.8.3 Flashbacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .118
7.9 Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .118
7.10 Maintenance of AA Spectrophotometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .118
7.11 AAS Performance Checks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .119
7.12 Sample Collection and Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .119
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Chapter 8 DIRECT ASPIRATION OR FLAME ATOMIC

ABSORPTION SPECTROMETRY (FAAS)
8.1 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .121
8.2 Direct Air–Acetylene Flame Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .121
8.2.1 General Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .121
8.2.2 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .121
8.2.3 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .122
8.2.4 Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .123
8.2.5 Standardization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .124
8.2.6 Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .124
8.2.7 Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .124
8.3 Direct Nitrous Oxide–Acetylene Flame Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .124
8.3.2 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .124
8.3.3 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .125
8.3.4 Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .125
8.3.5 Standardization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .126
8.3.6 Analysis of Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .126
8.3.7 Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .126
8.4 Interferences, Safety, and Quality Control Requirements in FAAS . . . . . . . . . . . . . . . . . .126
8.5 Maintenance of FAA Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .126
8.6 Performance Check of FAA Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .126
Chapter 9 GRAPHITE FURNACE ATOMIC

ABSORPTION SPECTROMETRY
9.1 General Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .129
9.1.1 Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .129
9.1.2 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .129
9.2 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .130
9.2.1 Atomic Absorption Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .130
9.2.2 Burner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .130
9.2.3 Hollow Cathode Lamps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .130
9.2.4 Graphite Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .130
9.2.5 Strip-Chart Recorder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .131
9.2.6 Water Supply for Cooling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .132
9.2.7 Sample Dispensers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .132
9.3 Analysis by Graphite Furnace Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .132
9.3.1 Sample Pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .132
9.3.2 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .132
9.3.3 Instrument Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .133
9.3.4 Multi-Step Temperature Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .133
9.3.5 Measuring the Graphite Furnace AA Signal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .134
9.3.6 Instrument Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .134
9.3.7 Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .134
9.3.8 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .135
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9.4 Interferences and the Graphite Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .135

9.4.1 Spectral Interference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .135
9.4.2 Nonspectral Interference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .137
9.5 Stabilized Temperature Platform Furnace (STPF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .139
9.6 Quality Control Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .140
9.7 Maintenance of Graphite Atomic Absorption Spectrophotometer . . . . . . . . . . . . . . . . . . .140
9.8 Performance Check of Graphite Atomic Absorption Spectrophotometer . . . . . . . . . . . . . .140
Chapter 10 COLD-VAPOR ATOMIC ABSORPTION

SPECTROMETRY
10.1.1 Advantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .143
10.1.2 Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .143
10.1.3 Detection Limit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .143
10.2 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
10.2.1 Atomic Absorption Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
10.2.2 Mercury Hollow Cathode Lamp (HCL) or Electrodeless Discharge Lamp (EDL)144
10.2.3 Recorder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
10.2.4 Absorption Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
10.2.5 Cell Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
10.2.6 Air Pump . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
10.2.7 Flowmeter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
10.2.8 Aeration Tubing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
10.2.9 Reaction Flask . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
10.2.10 Drying Tube . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .145
10.2.11 Connecting Tubing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .145
10.3 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .145
10.3.1 Sample Collection, Preservation, and Handling . . . . . . . . . . . . . . . . . . . . . . . . . .145
10.3.2 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .146
10.3.3 Instrument Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .147
10.3.4 Standardization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .147
10.3.5 Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .148
10.4 Interference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .149
10.4.1 Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .149
10.4.2 Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .149
10.4.3 Seawaters, Brines, and Industrial Effluents High in Chlorides . . . . . . . . . . . . . . . .150
10.4.4 Certain Volatile Organic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .150
10.6 Calculations and Reporting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .150
10.7 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .151
Chapter 11 HYDRIDE-GENERATION ATOMIC

ABSORPTION TECHNIQUE
11.1 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .153
11.1.1 Advantage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .153
11.1.2 Disadvantage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .153
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11.2 Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .153

11.2.1 Detection Limit and Concentration Range . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .154
11.3 Apparatuses and Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .154
11.3.1 Atomic Absorption Spectrometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .154
11.3.2 Arsenic and Selenium Hollow Cathode Lamp or Electrodeless Discharge Lamp .154
11.3.3 Background Correction at Measurement of Wavelength . . . . . . . . . . . . . . . . . . . . .154
11.3.4 Strip-Chart Recorder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .154
11.3.5 Atomizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .154
11.3.6 Reaction Cell for Producing As and Se Hydride . . . . . . . . . . . . . . . . . . . . . . . . . . .155
11.3.7 Eye-Dropper or Syringe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .155
11.3.8 Vent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .155
11.3.9 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .155
11.4 Interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .157
11.4.1 Possible Interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .157
11.5 Sample Collection, Preservation, and Handling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .158
11.6 Preparation of Samples and Standards for Total Arsenic and Selenium . . . . . . . . . . . . . . .158
11.7 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .158
11.7.1 Apparatus Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .158
11.7.2 Instrument Calibration Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .158
11.7.3 Determination of As and Se with Sodium Borohydride . . . . . . . . . . . . . . . . . . . . .159
11.7.4 Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .159
Chapter 12 INDUCTIVELY COUPLED PLASMA ATOMIC

EMISSION SPECTROSCOPY
12.1 Atomic Emission Spectroscopy (AES) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .161
12.1.1 Plasmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .161
12.1.2 Short History of AES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .161
12.2 General Characteristics of ICP-AES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .162
12.2.2 Performance Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .163
12.2.3 ICP Discharge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .165
12.3 ICP-AES Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .166
12.3.1 Sample Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .167
12.3.2 Emission Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .167
12.3.3 Collection and Detection of Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .168
12.3.4 Signal Processing and Instrument Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .169
12.3.5 Accessories for ICP-AES Instruments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .170
12.3.6 Instrument Care and Maintenance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .170
12.3.7 Verification of Instrument Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .171
12.4 Interferences in ICP-AES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .172
12.4.1 Spectral Interferences and Corrections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .172
12.4.2 Nonspectral Interference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .173
12.5 Reagents and Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .174
12.5.1 Chemicals, Standards, and Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .174
12.5.2 Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .174
12.5.3 Standard Stock Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .174
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12.5.4 Mixed Calibration Standard Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .174

12.5.5 Blanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .174
12.5.6 Instrument Check Standard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .175
12.5.7 Interference Check Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .175
12.5.8 Quality Control Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .175
12.5.9 Method Quality Control Sample . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .175
12.6 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .175
12.6.1 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .175
12.6.2 Instrument Setup and Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .175
12.6.3 Instrument Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .176
12.6.4 Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .176
12.6.5 Instrument Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .177
12.6.6 Method Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .177
12.6.7 Test for Matrix Interference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .177
12.6.8 Calculations and Corrections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .177
12.7 Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .178
Chapter 13 QUALITY CONTROL IN METALS ANALYSIS

13.2 Glassware Used in Metals Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .179
13.2.1 Volumetric Glassware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .179
13.2.2 Cleaning Glassware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .180
13.3 Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .180
13.4 Laboratory-Pure Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .180
13.4.1 Quality of Laboratory-Pure Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .180
13.4.2 Types of Laboratory-Pure Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .181
13.5 Field Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .181
13.5.1 Field QA/QC Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .182
13.5.2 Criteria for Field QC Checks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .182
13.6 Instrument Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .184
13.6.1 Calibration Stock and Standard Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .184
13.6.2 Calibration Check Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .186
13.6.3 Initial and Continuing Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .187
13.6.4 Accepted Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .188
13.6.5 Outline of Calibration Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .188
13.6.6 Special Calibration Criteria in Metals Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . .189
13.6.7 Summary of Definitions Related to Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . .189
13.7 Instrument Performance Check . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .190
13.7.1 Atomic Absorption Spectrophotometer (AAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . .191
13.7.2 Inductively Coupled Plasma Analyzer (ICP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .191
13.8 Laboratory QC Checks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .192
13.8.1 Blanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .192
13.8.2 Duplicate Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .192
13.8.3 Spikes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .193
13.8.4 Calibration Check Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .194
13.8.5 Blind QC Check Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .194
13.8.6 Performance Evaluation Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .194
13.8.7 Interference Check . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .194
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13.9 Detection Limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .194

13.9.1 Method Detection Limit (MDL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .194
13.9.2 Instrument Detection Limit (IDL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .195
13.9.3 Practical Quantitation Limit (PQL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .196
13.10 Accuracy and Precision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .196
13.10.1 General Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .196
13.10.2 Quality Control Delineation for Accuracy and Precision . . . . . . . . . . . . . . . . . .197
13.10.3 Quality Control Charts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .198
Chapter 14 SAMPLE COLLECTION FOR METALS ANALYSIS

14.1 General Considerations in Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .203
14.1.1 Factors and Requirements of Sampling Program To Be Considered . . . . . . . . . . .203
14.1.2 Preparation for Sample Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .203
14.1.3 Prefield Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .204
14.1.4 Types of Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .204
14.1.5 Manual and Automated Sample Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .204
14.1.6 General Rules in Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .205
14.1.7 Proper Material for Sampling Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .205
14.1.8 Errors Introduced during Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .205
14.1.9 Waste Disposal in the Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .205
14.2 Automatic Samplers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .205
14.2.1 Proper Operation of the Automatic Samplers . . . . . . . . . . . . . . . . . . . . . . . . . . . .205
14.2.2 Preparation of Sampling Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .206
14.3 Sample Containers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .206
14.3.1 Preferred Sample Containers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .206
14.3.2 Proper Cleaning of Sample Containers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .207
14.4 Sample Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .207
14.5 Special Sampling Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .207
14.5.1 Total Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .207
14.5.2 Dissolved Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .208
14.5.3 Suspended Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .208
14.5.4 Sample Collection of Hexavalent Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . .208
14.6 Holding Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .208
14.7 Field Records . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .208
14.7.1 Chain-of-Custody . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .208
14.7.2 Sample Label . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .209
14.7.3 Field Notebook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .209
14.7.4 Sample Field Log and Preservative Preparation Log . . . . . . . . . . . . . . . . . . . . . .212
14.7.5 Information Available in Field Records . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .212
14.8 Field Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .214
14.8.1 General Requirements of Field QA/QC Program . . . . . . . . . . . . . . . . . . . . . . . . .215
14.8.2 Field Quality Control Check Criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .215
14.9 Sample Collection from Different Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .216
14.9.1 Groundwater Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .216
14.9.2 Drinking Water Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .218
14.9.3 Sampling Surface Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .218
14.9.4 Sampling Waste Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .219
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14.9.5 Sampling Agricultural Discharges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .220

14.9.6 Collecting Domestic Sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .221
14.9.7 Collecting Soil Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .221
14.9.8 Sampling Hazardous Wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .222
14.9.9 Sampling Fish Tissues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .224
14.9.10 Collecting Air Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .224
Chapter 15 SAMPLE PREPARATION FOR METALS ANALYSIS

15.1.1 Sample Pretreatment for Total Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .227
15.1.2 Sample Pretreatment for Dissolved Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .227
15.1.3 Sample Pretreatment for Suspended Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .227
15.1.4 Preliminary Filtration of Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .227
15.1.5 Sample Pretreatment for Acid-Extractable Metals . . . . . . . . . . . . . . . . . . . . . . . . .228
15.2 Digestion Procedures for Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .228
15.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .228
15.2.2 Nitric Acid Digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .229
15.2.3 Nitric Acid–Hydrochloric Acid Digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .229
15.2.4 Nitric Acid–Sulfuric Acid Digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .230
15.2.5 Nitric Acid–Perchloric Acid Digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .230
15.2.6 Nitric Acid–Perchloric Acid–Hydrofluoric Acid Digestion . . . . . . . . . . . . . . . . . .231
15.2.7 Dry Ashing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .231
15.2.8 Microwave-Assisted Digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .231
15.3 Acid Digestion for Total and Dissolved Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233
15.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233
15.3.2 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233
15.3.3 Quality Control (QC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233
15.4 Acid Digestion of Aqueous Samples and Extracts for Total Metals by Flame
Atomic Absorption Spectrometry (FAAS) and Inductively Coupled
Plasma (ICP) Analyzer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .234
15.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .234
15.4.2 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .234
15.5 Acid Digestion of Aqueous Samples and Extracts for Total Metals by Graphite
Furnace Spectroscopy (GrAAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .234
15.5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .234
15.5.2 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .235
15.6 Sample Preparation for Arsenic and Selenium Determination by Graphite
Furnace Spectroscopy (GrAAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .235
15.6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .235
15.6.2 Procedure for Aqueous Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .235
15.6.3 Procedure for Solid Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .236
15.7 Sample Preparation for Silver Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .236
15.8 Sample Preparation for Antimony Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .236
15.9 Sample Preparation for Mercury Determination (Cold-Vapor Technique) . . . . . . . . . . . . .236
15.9.1 Preparation of Aqueous Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .236
15.9.2 Preparation of Solid and Semisolid Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . .237
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15.10 Acid Digestion of Sediments, Sludges, and Soils for Total Metals Analysis . . . . . . . . . .237
15.10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .237
15.10.2 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .237
15.10.3 Quality Control (QC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .238
15.11 Dissolution Procedure for Oils, Greases, and Waxes . . . . . . . . . . . . . . . . . . . . . . . . . . . .239
15.11.1 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .239
15.11.2 Sample Collection, Preservation, and Handling . . . . . . . . . . . . . . . . . . . . . . . . .239
15.11.3 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .239
15.12 Sample Preparation for Hexavalent Chromium (Chelation/Extraction) . . . . . . . . . . . . . .239
15.12.1 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .240
15.12.2 Chelation and Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .240
15.13 Extraction Procedure (EP) Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .241
15.13.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .241
15.13.2 Sample Collection, Preservation, and Handling . . . . . . . . . . . . . . . . . . . . . . . . .241
15.13.3 Apparatus and Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .241
15.13.4 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .242
15.13.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .242
15.14 Extraction Procedure for Oily Wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .244
15.14.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .244
15.14.2 Interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .244
15.14.3 Apparatus and Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .244
15.14.4 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .245
15.14.5 Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .245
15.14.6 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .245
15.15 Documentation during Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .246
15.16 Disposal of Samples, Digestates, Extracts, and Other Wastes . . . . . . . . . . . . . . . . . . . . .246
Chapter 16 CONVERTING RAW DATA INTO

REPORTABLE FORM
16.1 Responsibilities of the Analyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .249
16.2 Calculations for Final Values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .250
16.2.1 Dilution and Concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .251
16.2.2 Calculations for Solids, Moisture, and Ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .251
16.2.3 Conversion of Milligrams per Liter and Milliequivalents per Liter . . . . . . . . . . . .252
16.2.4 Conversion of ppm (w/v) to mg/cm3 and Vice Versa . . . . . . . . . . . . . . . . . . . . . . . .252
16.2.5 Significant Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .255
16.2.6 Rounding Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .255
16.2.7 Exponential Notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .256
16.3 Records for Raw and Calculated Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .256
16.3.1 Field and Laboratory Notebook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .256
16.3.2 Work Sheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .256
16.3.3 Other Documentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .256
16.3.4 Documents To Be Saved . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .256
16.4 Evaluation and Approval of Analytical Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .260
16.4.1 Checking Correctness of Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .260
16.4.2 Validation of QC Checks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .260
16.4.3 Documentation of Out-of-Control Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . .263
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Chapter 17 REPORTING ANALYTICAL DATA

17.1 Required Documentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .265
17.1.1 Documentation Required To Approve and Defend Reported Data . . . . . . . . . . . . .265
17.2 Significant Figures in Analytical Reports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .266
17.3 Units Used To Express Analytical Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .266
17.4 Confidence Interval . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .267
17.5 Report Format . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .267
Chapter 18 SELECTED METHODS FOR DETERMINATION

OF METALS IN ENVIRONMENTAL SAMPLES
18.1 Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .269
18.1.1 EPA-Approved Methods and References for Analyzing Water Samples . . . . . . . .269
18.1.2 EPA-Approved Methods and References for Analyzing
Sediments and Residuals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .270
18.1.3 Approved Modification of EPA Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .270
18.1.4 EPA Contract Laboratory Protocol (CLP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .271
18.1.5 Determination of Selected Metals in Environmental Samples . . . . . . . . . . . . . . . .271
18.2 Aluminum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .271
18.2.1 Flame Atomic Absorption Spectroscopy (FAAS) . . . . . . . . . . . . . . . . . . . . . . . . . .272
18.2.2 Graphite Furnace Atomic Absorption Spectrometry (GrAAS) . . . . . . . . . . . . . . . .273
18.3 Antimony . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .273
18.4 Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .274
18.4.1 Gaseous Hydride Atomic Absorption Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . .275
18.5 Barium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .276
18.6 Beryllium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .277
18.7 Bismuth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .279
18.8 Cadmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .279
18.9 Calcium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .280
18.9.2 Determination of Hardness by EDTA Titrimetric Method . . . . . . . . . . . . . . . . . . .281
18.9.3 Calcium Determination by EDTA Titrimetric Method . . . . . . . . . . . . . . . . . . . . . .284
18.10 Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .285
18.10.1 Flame Atomic Absorption Spectroscopy (FAAS) . . . . . . . . . . . . . . . . . . . . . . . .285
18.10.2 Graphite Furnace Atomic Absorption Spectrometry (GrAAS) . . . . . . . . . . . . . .286
18.11 Hexavalent Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .286
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18.11.1 Chelation/Extraction Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .286

18.11.2 Colorimetric Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .288
18.12 Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .289
18.12.1 Graphite Furnace Atomic Absorption Spectrometry (GrAAS) . . . . . . . . . . . . .290
18.13 Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .290
18.14 Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .291
18.15 Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .292
18.16 Lithium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .293
18.17 Magnesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .293
18.18 Manganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .293
18.19 Mercury . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .294
18.19.1 Cold-Vapor Atomic Absorption Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . .294
18.20 Molybdenum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .294
18.21 Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .296
18.22 Potassium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .296
18.23 Selenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .297
18.23.2 Atomic Absorption Gaseous Hydride Technique . . . . . . . . . . . . . . . . . . . . . . . .299
18.24 Silver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .299
18.25 Sodium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .300
18.26 Thallium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .300
18.27 Tin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .301
18.28 Vanadium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .302
18.29 Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .303
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Chapter 19 Laboratory Safety Rules

19.1 Laboratory Hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .305
19.1.1 Chemical Hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .305
19.1.2 Fire Hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .307
19.1.3 Carelessness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .308
19.2 Safe Handling of Compressed Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .309
19.2.1 General Precautions When Working with Compressed Gases . . . . . . . . . . . . . . . .309
19.2.2 Hazardous Properties of Compressed Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .310
19.3 Stockroom Safety Rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .310
19.3.1 Safety Checklist for Storage Rooms: Room Characteristics and Organization . . .310
19.3.2 Chemical Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .310
19.4 Summary of Laboratory Safety Rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .311
APPENDICES
Appendix A: Operation of Mass Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .313
Appendix B: Silicon Chips . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .317
Appendix C: Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .321
Appendix D: Metals and Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .323
Appendix E: Toxicity of Cyanide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .333
Appendix F: Components of Nucleic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .335
Appendix G: Polarized Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .339
Appendix H: Stock Metal Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .341
Appendix I: Calculation for Solid Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .345
Appendix J: Plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .347
Appendix K: Soxhlet Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .349
Appendix L: SI Units and Conversion Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .351
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .353
INDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .355
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Introduction to Metals
1
1.1 INTRODUCTION TO ELEMENTS
1.1.1 MATTER
Matter is anything that has mass and occupies space. Matter is found in many different forms, and
every year thousands of new types of matter are synthesized. Matter is grouped into two major
classes: pure substances and mixtures. Pure substances are subdivided into elements and compounds.
Elements are pure substances that cannot be decomposed by chemical changes. Compounds are pure
substances that can be decomposed chemically.
1.1.2 Elements
Elements are the basic units of matter. At present, 109 elements have been identified; 92 occur in na-
ture, and the rest are synthetic. At 25°C, 97 elements are solids, 2 are liquids, and 11 are gases.
1.1.2.1 Element Symbols

Element symbols are usually derived from the first one or two letters of the element’s name. Twelve
of the elements have one-letter symbols that correspond to the first letter of the element’s name: hy-
drogen (H), boron (B), carbon (C), nitrogen (N), oxygen (O), fluorine (F), phosphorus (P), sulfur (S),
vanadium (V), yttrium (Y), iodine (I), and uranium (U). Other elements are designated by one-letter
symbols but do not correspond to the first letter of their English-language names. K is the symbol for
potassium, which is the first letter of its Latin name, kalium, which means ashes. Similarly, the sym-
bol for tungsten is W, derived from the Latin word wolframate. Most of the remaining elements have
been assigned two-letter symbols. The first letter is always an uppercase letter, and the second, a low-
ercase letter. For instance, the symbol for cobalt is Co, not CO. Some symbols are made up of the
first two letters of the element’s English-language name, others consist of two letters from a Latin
word, and the remainder combine the first letter of the element with some other letter in the name.
1.1.2.2 Element Names

The origins of element names are diverse, including geographical locations, the names of great sci-
entists, mythological gods, and astronomical bodies. Table 1.1 lists the names and symbols of ele-
ments derived from Latin words, and Table 1.2 contains the origins of selected elements. The sym-
bol of an element in the periodic table is accompanied by a whole number and a decimal number. To
understand the significance of these numbers, a short review of atomic structure is necessary.
1
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2 Environmental Sampling and Analysis for Metals
TABLE 1.1
Names and Symbols of Elements Derived from
Latin Words
Name Symbol Latin Word
Antimony Sb Stibium
Gold Au Aurum
Lead Pb Plumbum
Mercury Hg Hydrargyrum
Potassium K Kalium
Silver Ag Argentum
Tin Sn Stannum
Tungsten W Wolframe
TABLE 1.2
Origins of Selected Element Names
Element Symbol Origin of Name
Location
Americium Am America
Berkelium Bk Berkeley, CA
Californium Cf California
Europeum Eu Europe
Francium Fc France
Germanium Ge Germany
Polobnium Po Poland
Stroncium Sc Strontia, Scotland
Scientist
Curium Cm Marie and Pierre Curie
Einsteinium Es Albert Einstein
Fermium Fm Enrico Fermi
Lawrencium Lr Ernest O. Lawrence
Mendelevium Md Dmitri Mendeleev
Nobelium No Alfred Nobel
God or Astronomical Body

Helium He Greek “helios” (sun)
Niobium Ni Niobe, daughter of Tantalus
Neptunium Np Neptune
Palladium Pd Asteroid called Pallas
Plutonium Pu Pluto
Selenium Se Greek selene (moon)
Thorium Th Thor
Uranium U Uranus
1.1.3 ATOMS
Atoms are the smallest particles that retain the chemical properties of elements. In other words, an
atom is the smallest unit of an element, and each element is composed of similar atoms. Atoms are
extremely small; for example, 1 g of carbon (C) contains 5 × 1022 C atoms.
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Introduction to Metals 3
FIGURE 1.1 Typical atom. Protons and neutrons make up the nucleus;
electron “clouds” surround the nucleus.
1.1.3.1 Subatomic Particles

Atoms are composed of three fundamental particles — protons, electrons, and neutrons. (Figure 1.1
illustrates a typical atom.) Particles are characterized by mass and electric charge. Protons and neu-
trons have approximately the same mass, 1.67 × 10–24 g. The mass of an electron is only 9.11 × 10–28 g,
about 1/1837th of a proton or a neutron; in other words, 1837 electrons are needed to equal the mass
of one proton. Electrons are negatively charged (1−). Protons possess the same charge as
electrons, but it is positive (1+). Neutrons have no charge and are thus electrically neutral. Because an
atom is electrically neutral, the number of protons should be equal to the number of electrons. Masses
of subatomic particles are frequently expressed using a relative unit, known as a unified atomic mass
unit (u): 1 u = 1.6606 × 10–24 g. Properties of subatomic particles are presented in Table 1.3.
Protons and neutrons are located in a very small region of the atom, called the nucleus, and are
surrounded by electrons. Electrons are located outside of the nucleus in quantized energy levels. Each
energy level is divided into smaller regions called sublevels, and each sublevel is divided into or-
bitals, the location of the electrons. The exact definition of the orbital is a volume of space where
there is a specific probability of encountering electrons.
According to the Heisenberg’s uncertainty principle, it is impossible to accurately determine
the exact position and velocity of an electron. Each orbital contains a maximum of two electrons,
which spin in opposite directions. Each energy level contains a precise number of sublevels and
the sublevels contain a precise number of orbitals; thus, each sublevel contains a specified number
of electrons.
1.1.3.2 Atomic Number

The atomic number of an atom equals the number of protons (+) in the nucleus of an atom, be-
cause in a neutral atom the number of protons (+) should be equal to the number of electrons (-).
Therefore,
Atomic number = number of protons (+) = number of electrons (–)
TABLE 1.3
Properties of Subatomic Particles
Particle Symbol Mass (g) Mass (u) Relative Charge
Proton p+ 1.6726 × 10–24 1.007276 1+
Neutron no 1.6749 × 10–24 1.008666 0
Electron e–1 9.1096 × 10–28 0.00054861 −
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1.1.3.3 Mass Number

The mass number of an atom equals the total number of protons (+) and neutrons (o) in the nucleus:
Mass number = number of protons + number of neutrons

Number of neutrons (no) = mass number – atomic number
1.1.3.4 Atomic Mass and Atomic Weight

The atomic mass of an element is the average mass of its naturally occurring isotopes relative to the
mass of C612. Most elements are found in nature as mixtures of isotopes in a more or less constant ratio.
For some elements, these ratios vary slightly, but for most purposes the slight variations can be ignored.
The atomic weight of an element is a weighted average of the combined mass of the isotopes.
The mass of an isotope is approximately the same as its mass number. Some elements — for exam-
ple, gold, fluorine, and aluminum — occur naturally as a single isotope. The atomic weights of these
elements are, of course, close to whole numbers (gold, 196.7; fluorine, 18.998; and aluminum,
26.98). The atomic masses of the elements are decimal numbers. The elements and their atomic num-
bers and atomic masses are listed in Table 1.4.
1.1.4 ISOTOPES
Isotopes are atoms with the same number of protons but a different number of neutrons in their nu-
clei; that is, they have the same atomic number but different mass numbers. A large percentage of the
elements are composed of mixtures of different isotopes. For example, three isotopes of uranium
occur naturally: U92234 contains 142 neutrons, U92235 contains 143 neutrons, and the third isotope, U92238, has
146 neutrons. Mass spectroscopy is used to measure relative atomic mass and isotopes. (See
Appendix A for a description of mass spectrophotometer operations.)
1.2 PERIODIC TABLE OF ELEMENTS

The periodic table of elements is a tabular arrangement of elements in rows and columns, highlight-
ing the regular repetition of properties of the element. In 1869, Russian chemist Dmitri Mendeleev
and German chemist Lothar Meyer, working independently, made similar discoveries. They found
that when they arranged the elements in order of atomic weight, they could place them in horizontal
rows, one row under the other, so that the elements in any one vertical column have similar proper-
ties. In the early part of the twentieth century, scientists demonstrated that the elements are charac-
terized by respective atomic numbers. A modern version of the periodic table, with the elements
arranged by atomic numbers, is shown in Table 1.5.
The basic structure of the periodic table is its division into rows and columns, or periods and
groups. A period consists of the elements in any one horizontal row of the periodic table, and a group
consists of the elements in any one column of the periodic table. The groups are numbered with
Roman numerals, and A’s and B’s are common. In Europe, a similar convention has been used but
the A’s and B’s are interchanged in some columns. To eliminate this confusion, the International
Union of Pure and Applied Chemistry (IUPAC) recommended that the groups be numbered consec-
utively from 1 to 18. Each period is numbered consecutively from 1 to 7. The periodic table of ele-
ments is probably the most important table in chemistry. A modern version of the periodic table, with
the elements arranged by atomic numbers and the group numbers by traditional and IUPAC conven-
tions, is presented in Table 1.5.
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TABLE 1.4
Table of Elements with Atomic Numbers and Atomic Masses
Atomic Atomic Atomic Atomic
Name Symbol Number Mass Name Symbol Number Mass
Actinium Ac 89 227.0278a Molybdenum Mo 42 95.94
Aluminum Al 13 26.98154 Neodymium Nd 60 144.24
Americium Am 95 243a Neon Ne 10 20.179
Antimony Sb 51 121.75 Neptunium Np 93 237.0482
Argon Ar 18 39.948 Nickel Ni 28 58.70
Arsenic As 33 74.9216 Niobium Nb 41 92.9064
Astatine At 85 210a Nitrogen N 7 14.0067
Barium Ba 56 137.33 Nobelium No 102 259a
Berkelium Bk 97 247a Osmium Os 76 190.2
Beryllium Be 4 9.01218 Oxygen O 8 15.9994
Bismuth Bi 83 208.9804 Palladium Pd 46 106.4
Boron B 5 10.81 Phosphorus P 15 30.97376
Bromine Br 35 79.904 Platinum Pt 78 195.09
Cadmium Cd 48 112.41 Plutonium Pu 94 244a
Calcium Ca 20 40.08 Polonium Po 94 209a
Californium Cf 98 251a Potassium K 19 39.0983
Carbon C 6 12.011 Praeseodymium Pr 59 140.9077
Cerium Ce 58 140.12 Promethium Pm 61 145a
Cesium Cs 55 132.9054 Protactinium Pa 91 231.0359
Chlorine Cl 17 35.453 Radium Ra 88 226.0254
Chromium Cr 24 51.996 Radon Rn 86 222a
Cobalt Co 27 58.9332 Rhenium Re 75 186.207
Copper Cu 29 63.546 Rhodium Rh 45 102.9055
Curium Cm 96 247a Rubidium Rb 37 85.4678
Dysprosium Dy 66 162.50 Ruthenium Ru 44 101.07
Einsteinium Es 99 252a Samarium Sm 62 150.4
Erbium Er 68 167.26 Scandium Sc 21 44.9559
Europium Eu 63 151.96 Selenium Se 34 78.96
Femium Fm 100 257a Silicon Si 14 28.0855
Fluorine F 9 18.998403 Silver Ag 47 107.868
Francium Fr 87 223a Sodium Na 11 22.98977
Gadolinium Gd 64 157.25 Strontium Sr 38 87.62
Gallium Ga 31 69.72 Sulfur S 16 32.06
Germanium Ge 32 72.59 Tantalum Ta 73 180.9479
Gold Au 79 196.9665 Technetium Tc 43 98a
Hafnium Hf 72 178.49 Tellurium Te 52 127.60
Helium He 2 4.00260 Terbium Tb 65 158.9254
Holmium Ho 67 164.9304 Thallium Tl 81 204.37
Hydrogen H 1 1.0079 Thorium Th 90 232.0381
Indium In 49 114.82 Thulium Tm 69 168.9342
Iodine I 53 126.9045 Tin Sn 50 118.69
Iridium Ir 77 192.22 Titanium Ti 22 47.90
Iron Fe 26 55.847 Tungsten W 74 183.85
Krypton Kr 36 83.80 Unnilhexium Unh 106 263a
Lanthanum La 57 138.9055 Unnilpentium Unp 105 262a
Lawrencium Lr 103 260a Unnilquadium Unq 104 261a
Lead Pb 82 207.2 Uranium U 92 238.029
Lithium Li 3 6.941 Vanadium V 23 50.9415
Lutetium Lu 71 174.967 Xenon Xe 54 131.30
Magnesium Mg 12 24.305 Ytterbium Yb 70 173.04
Manganese Mn 25 54.9380 Yttrium Y 39 88.9059
Mendelevium Md 101 258a Zinc Zn 30 65.38
Mercury Hg 80 200.59 Zirconium Zr 40 91.22
a
Not naturally occurring.
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Periodic Table of the Elements

TABLE 1.5
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The IA–VIIIA groups, or 1, 2, 13, 14, 15, 16, 17, and 18, are called the main groups or repre-
sentative elements. The B groups, or 3 to 12, are called the transition elements. The two rows of el-
ements at the bottom are called the inner-transition elements, where the first row is referred to as the
lanthanides with atomic numbers 58 to 71, and the second row is known as the actinides with atomic
numbers 90 to 103.
The elements in a group have similar properties:
• Elements in group IA (1), except hydrogen (H), are called alkali metals.
• Elements in group IIA (2) are called alkaline earth metals.
• Group B elements (1–12) are the transition elements. This group contains the most com-
mon metallic elements.
• Group IIIA (13) lacks a unique name and is often called the aluminum or boron-aluminum
group.
• Groups IVA (14) and VA (15) are designated as the carbon and nitrogen groups, respec-
tively.
• For group VIA (16), an old name, the chalcogens, is used.
• Group VIIA (17) is known as the halogens.
• Group VIIIA (18) contains the noble gases.
The periodic table with group names is shown in Table 1.6.

Each block contains a single element name and the element’s atomic number (whole number)
and atomic weight (decimal number), as illustrated in Figure 1.2.
The group numbers of the representative elements in the periodic table, IA (1) through VIIIA
(18), indicate the number of electrons in the outer energy level, called the valence shell. The period
number is equal to the number of the outer energy level.
Group VIIIA (18) elements exist as gases, which consist of uncombined atoms (e.g., neon, Ne).
The outer energy levels of gases contain eight electrons. For a long time these elements were con-
sidered chemically inert because no compounds were known. Then, in the early 1960s, several com-
pounds of xenon were formed. At present, compounds for krypton and radon are also known.
The elements in Group VIIIA are known as noble gases because of their relative poor reactivity.
The tendency of atoms in molecules to have eight electrons on valence shells is known as the octet
rule. The number of electrons that must be lost or gained in order for an atom to have the eight-elec-
tron configuration on the outer energy level is called valence. When an atom loses electrons it be-
comes a positively charged ion, or cation, and when an atom gains electrons it becomes a negatively
charged ion, or anion.
FIGURE 1.2 Each block in the periodic table contains information on one element.
L1572_C01
TABLE 1.6
Periodic Table with Names of Chemical Groups
5/23/02
1:16 PM
Group
IA(1) VIIIA(18)
Page 8
1 H
IIA(2) IIIA(13) IVA(14) VA(15) VIA(16) VIIA(17)
VIIIB
3
IIIB(3) IVB(4) VB(5) VIB(6) VIIB(7) (8) (9) (10) IB(11) IIB(12)
Period
4
Halogens
5
Noble gases
Alkali metals
Chalcogens
Transition metals
Alkaline earth metals

Carbon-silicon group
Boron aluminum group
6
Nitrogen-phosphorus group
Lanthanide series
Actinide series
Environmental Sampling and Analysis for Metals
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TABLE 1.7
Metals, Nonmetals, and Metalloids Located on the
Periodic Table
Metalloids Nonmetals
Metals
1.3 PROPERTIES OF METALS, NONMETALS, AND METALLOIDS

The elements of the periodic table are divided by a heavy “staircase” line into metals on the left and
nonmetals on the right. Most of the elements bordering the staircase line in the periodic table are met-
alloids, or semimetals, as shown in Table 1.7.
1.3.1 METALS
Metals are substances that have a characteristic luster or shine and are good conductors of heat and
electricity; except for mercury (Hg), the metallic elements are solids at room temperature. They are
more or less malleable (can be hammered or rolled into thin sheets) and ductile (can be drawn into
wire). For example, the production of sheet steel for automobiles and household appliances depends
on the malleability of iron and steel, and the manufacture of electrical wire is based on the ductility
of copper.
Mercury’s low melting point (−39°C) and fairly high boiling point (357°C) make it useful as a fluid
in thermometers. Most of the other metals have much higher melting points. Tungsten (W) has the high-
est melting point of any metal (3400°C), which explains its use as a filament in electric light bulbs.
An important physical property of metals is hardness. Some metals, such as iron and chromium,
are very hard, but others, such as copper and lead, are rather soft. The alkali metals are so soft that
they can be cut with a knife.
Chemically, metals tend to lose electrons to form positive ions. The special properties of metal re-
sult from delocalized bonding, in which bonding electrons are spread over a number of atoms. A very
simple picture of a metal depicts an array of (+) ions surrounded by a “sea” of valence electrons (−)
that are free to move over the entire metal crystal. The electron sea model is presented in Figure 1.3.
The hardness and malleability of metals are explained by the strong electrostatic attraction
among positive nuclei and negative electrons; the cations can be easily moved as the metal is ham-
mered into sheet or pulled into wire. Electrical conductivity results from the delocalization of outer
electrons; when the metal is connected to a source of electric current, the electrons easily move away
from the negative side of the electric source and toward the positive side, forming an electric current
in the metal.
1.3.2 NONMETALS
A nonmetal is an element that does not exhibit the characteristics of a metal. Most of the nonmetals
are gases (e.g., chlorine, Cl2, and oxygen, O2), or solids (e.g., sulfur, S, and phosphorus, P). The solid
nonmetals are usually hard, brittle substances. Bromine is the only liquid nonmetal. Table 1.8 shows
the differences between metals and nonmetals.
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Positive ions from the metal
Electron cloud that

does not belong to
any one metal ion
FIGURE 1.3 Electron sea model.
1.3.3 METALLOIDS OR SEMIMETALS

A metalloid or semimetal is an element having both metallic and nonmetallic properties. In most re-
spects, metalloids behave as nonmetals, both chemically and physically. However, in their most im-
portant physical property, electrical conductivity, they somewhat resemble metals. Metalloids tend to
be semiconductors; they conduct electricity but not nearly so well as metals. These elements, such as
silicon (Si) and germanium (Ge), are good semiconductors — when pure, they are poor conductors
of electricity at room temperature, but moderately good conductors at higher temperatures. The elec-
trical conductivity of a semiconductor is greatly enhanced by adding small amounts of certain ele-
ments to it, a process known as doping.
Doped semiconductors have useful properties in the manufacture of solid-state electronic devices.
Silicon is a basic material of the solid-state electronic industry. Television receivers, microcomputers, and
other electronic equipment employ miniature electrical circuits built on silicon chips (see Appendix B).
TABLE 1.8
Characteristics of Metals and Nonmetals
Metals Nonmetals
Physical Properties
Good conductors of electricity Poor conductors of electricity
Ductile Not ductile
Malleable, lustrous Not malleable
Solids Solids, liquids, or gases
High melting point Low melting point
Good conductors of heat Poor conductors of heat
Chemical Properties
React with acids Do not react with acids
Form basic oxides that react with acids Form acidic oxides that react with bases
Form cations Form anions
Form ionic halides Form covalent halides
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1.4 EARLY HISTORY OF METAL USE

The special properties of metals played an important role in the development of human society. In
the Copper Age, humans discovered that copper (Cu), found on the surface of the Earth, could be
hammered into sheets, which were then used in the manufacture of numerous useful artifacts. Later
it was discovered that rocks containing copper (Cu) and tin (Sn) compounds yielded bronze (the first
manufactured alloy), so around 4000 BC the Bronze Age began. The first raw iron (Fe) was found in
meteorites (the first name of iron was “metal from heaven”), and later, around 2500 BC, iron was
smelted from ores, and hence the Iron Age began. Around 100 BC in India, the first steel (90–95%
iron and 5–10% carbon) objects appeared. Metallurgy arose from these beginnings. Metallurgy is the
scientific study of the production of metals from ores and the manufacture of alloys with various use-
ful properties.
1.5 SOURCES OF METALS AND THEIR COMPOUNDS

Metals occur in nature in many different forms. Most are found in compounds, either in the Earth’s
crust or in the ocean, although some of the less reactive metals are found in the uncombined state
(e.g., gold).
Localized deposits of certain metal compounds are called ores. An ore is simply a mineral de-
posit that has a desirable component in a sufficiently high concentration to make its extraction eco-
nomical. For example, magnesium is found in the mineral called olivine (Mg2SiO4) with a 30% mag-
nesium (Mg) content. Magnesium concentration in seawater is only 0.3%, but the principal source of
magnesium is seawater because it is much more economical to extract it from seawater. The two most
abundant metals in seawater are sodium (Na) and magnesium (Mg). Separation of Mg from seawa-
ter takes advantage of the low solubility of magnesium hydroxide, Mg(OH)2. Another potential
source of metals from the sea is the mining of manganese nodules from the ocean floor. Manganese
(Mn) nodules are lumps about the size of an orange that contain significant amounts of Mn (about
25%) and iron (Fe) (about 15%). Metal extraction from the oceans is a recent phenomenon. As was
mentioned above, metallurgists study the production of metals from their sources, including mining,
separation, and preparation for use.
1.6 SOURCES OF METAL POLLUTION

1.6.1 METAL POLLUTION FROM MINING AND PROCESSING ORES
Digging a mine, removing ore from it, and extraction and processing of the minerals sometimes cause
environmental damage. For example, mining operations can destroy habitat, farmland, and homes;
produce soil erosion; and pollute waterways via toxic drainage. Emission of toxic materials from
smelters — arsenic (As), selenium (Se), lead (Pb), cadmium (Cd), and sulfur oxides, among others
— causes serious air pollution. Surface mining produces about eight times as much waste as under-
ground mining, but deep mining can produce even worse problems, such as earthquakes. When un-
derground mines cave in, not only do they kill miners but they also cause subsidence of the surface,
forming holes into which roads and houses may collapse. As near-surface minerals are depleted, min-
ers have to dig deeper to find the mineral. A study by the National Academy of Science predicted that
copper (Cu) mining operations in the year 2000 would produce three times as much waste per ton of
copper output compared to the same activities in 1978.
Exposure of pyrite (FeS) and other sulfide minerals to atmospheric oxygen and moisture results
in oxidation of this mineral and the formation of acid-mine drainage water. The release of acid-mine
drainage from active and abandoned mines, particularly coal mines, has been widely associated with
L1572_C01 5/23/02 1:16 PM Page 12
serious water quality problems. It dissolves toxic elements from tailings and soils and carries them
into waterways and even groundwater. Water quality problems involve relatively high levels of met-
als such as iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), nickel (Ni), and cobalt (Co).
Ore processing, smelting, and refining operations can cause deposition of large quantities of trace
metals, such as lead (Pb), zinc (Zn), copper (Cu), arsenic (As), and silver (Ag), into drainage basins
or direct discharge into aquatic environments.
1.6.2 OTHER SOURCES OF METAL POLLUTION

1.6.2.1 Domestic Wastewater Effluents
Domestic wastewater effluents contain large amounts of trace metals from metabolic waste products,
corrosion of water pipes — copper (Cu), lead (Pb), zinc (Zn), and cadmium (Cd), and household
products, such as detergents — iron (Fe), manganese (Mn), chromium (Cr), nickel (Ni), cobalt (Co),
zinc (Zn), boron (B), and arsenic (As). Wastewater treatment usually removes less than 50% of the
metal content of the influent, leaving the effluent with significant metal loading. The sludge result-
ing from wastewater treatment is also rich in metals. Domestic wastewater and the dumping of do-
mestic and industrial sludge are the major artificial sources of cadmium (Cd), chromium (Cr), cop-
per (Cu), iron (Fe), lead (Pb), and mercury (Hg) pollution.
1.6.2.2 Stormwater Runoff

Stormwater runoff from urbanized areas is a significant source of metal pollution in the receiving wa-
ters. Metal composition of urban runoff water is dependent on many factors, such as city planning,
traffic, road construction, land use, and the physical characteristics and climatology of the watershed.
1.6.2.3 Industrial Wastes and Discharges

Metals and their concentrations in industrial wastes and discharges are specific and depend on the
profile of a specific industry.
1.6.2.4 Sanitary Landfills

The metal contents and average concentrations of sanitary-landfill leachates are Cu (5 ppm), Zn (50
ppm), Pb (0.3 ppm), and Hg (60 ppb).
1.6.2.5 Agricultural Runoff

The metal content of agricultural runoff originates in sediments and soils saturated by animal and
plant residues, fertilizers, specific herbicides and fungicides, and use of sewage and sludge as plant
nutrients.
1.6.2.6 Fossil Fuel Combustion

Fossil fuel combustion is a major source of airborne metal contamination of natural waters.
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Discussion of Metallic Elements

2
2.1 REPRESENTATIVE ELEMENTS
As discussed in Chapter 1, in the traditional numbering system of the periodic table, the A group el-
ements are called main groups or representative elements. Only a few metallic elements occur in na-
ture as free metals. All seven metallic elements known to the ancients (gold, silver, copper, iron, lead,
mercury, and tin) have been found in the metallic state. Metals are too reactive chemically to be found
in quantity as metallic elements. Except for gold, the metallic elements are obtained principally from
their naturally occurring solid compounds or ores. A major source of metals and their compounds is
the Earth’s crust.
Minerals are naturally occurring inorganic substances or solid solutions with a definite crys-
talline structure. Thus, a mineral might be a definite chemical substance, or it might be a homoge-
neous solid mixture. Rock is a naturally occurring solid material composed of one or more minerals.
An ore is a rock or mineral from which a metal or nonmetal can be economically produced.
Representative metal groups are listed below.
Group IA (1): lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs),
francium (Fr)
Group IIA (2): beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba),
radium (Ra)
Group IIIA (3): aluminum (Al), gallium (Ga), indium (In), thallium (Tl)
Group IVA (4): tin (Sn), lead (Pb)
Group VA (5): bismuth (Bi)
2.1.1 GROUP IA (1): ALKALI METALS

Alkali metals are soft and the most reactive of all metals; they are never found as free elements in na-
ture, as they always occur in compounds. The pH of their aqueous solution is alkaline. All alkali met-
als are typically metallic in character, with a bright luster and high thermal and electrical conductiv-
ity. They have low densities because they have large atoms; large atoms lead to small ratios of mass
per volume (density = mass/volume). When ions of an alkali metal are added to a flame, the result-
ing brilliant colors are characteristic of the element’s atomic spectrum. For example, sodium salts are
bright yellow, potassium salts impart a pale violet color to the flame, and lithium salts give a beauti-
ful, deep-red color. All alkali metal salts are water soluble.
2.1.1.1 Lithium (Li)

Lithium is a soft, very rare metal. The source of lithium metal is the ore spodumene (LiAl(SiO3)2),
a lithium aluminum-silicate mineral. In recent years, the commercial importance of lithium has
risen markedly. Lithium is used in the production of low-density aluminum alloys for aircraft
13
13
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construction, and batteries with lithium metal anodes are also common. Advantages of lithium bat-
teries compared to other battery cells include relatively high voltages (about 3.0 V vs. 1.5 V) and
typically more electrical energy per mass of reactant, because of lithium’s higher voltages and low
atomic weight. Lithium hydroxide (LiOH) is used to remove carbon dioxide from the air in space-
craft and submarines. Lithium-6 deuteride is reportedly the fuel used in nuclear fusion bombs. The
Li+ ion is used in the treatment of mental disorders; for example, lithium carbonate (Li2CO3) for
treatment of manic depression. Other lithium compounds are used in the preparation of antihista-
mines and other pharmaceuticals.
2.1.1.2 Sodium (Na)

Sodium is the most familiar alkali metal. Sodium compounds are of enormous economic importance.
Common table salt (sodium chloride) has been an important article of commerce since prehistoric
times. Salt was of such importance in the Roman Empire that a specific allowance of salt was part of
soldiers’ pay. The word “salary” derives from the Latin salarium (salt) for this salt allowance. Major
industrial uses of sodium compounds include the manufacturing of glassware, detergents, paper, and
textiles. Soda ash (sodium carbonate, Na2CO3) is widely used in water treatment, such as for soften-
ing and increasing pH levels. It is also used in organic synthesis, sodium lamps, and photoelectric
cells. Household bleach is a 5% solution of sodium hypochlorite (NaOCl). An everyday household
chemical is sodium bicarbonate (baking soda, NaHCO3). Sodium has shown promise as a coolant in
certain kinds of nuclear reactors. It has a low melting point and a reasonably high boiling point, and
it conducts heat well. Sodium can be pumped through the reactor, where it readily picks up heat, and
then pumped through a heat exchanger, where the heat is removed.
Sodium is a natural constituent of water, but its concentration increases with pollution. Sodium
salts are extremely soluble in water and, when the element leaches from soil or is discharged into
streams by industrial waste processes, it remains in solution. Long-term excessive sodium consump-
tion is responsible for high blood pressure, and consumption of drinking water with high sodium con-
tent can be harmful to people with cardiac, circulatory, and renal diseases. In contrast, insufficient re-
placement of salt leached from the body as a result of sweating will lead to salt depletion, character-
ized by fatigue, nausea, giddiness, vomiting, and exhaustion. Sodium sulfate decahydrate (Na2SO4.10
H2O), known as Glauber salt, is used as a laxative. Therefore, water containing a high level of sodium
sulfate is not recommended for drinking. The American Heart Association recommends a sodium
level of less than 20 mg/l for drinking water. Excess sodium concentrations (over 2000 mg/l) in water
used by animals for drinking may also be toxic.
Irrigation water with a high sodium level can cause a displacement of exchangeable cations (Ca2+,
Mg ) followed by replacement of the cations by Na. The ratio of Na+ ions to total cation contents can
2+
be used for assessing the suitability of water for irrigation. The ability of water to expel calcium and
magnesium by sodium can be estimated by calculating the sodium absorption ratio (SAR).
Calculation and acceptance criteria are discussed in Section 4.4. With a few exceptions (e.g., sea-
weed), sodium ions tend to be toxic to plants.
2.1.1.3 Potassium (K)

Potassium, which has properties similar to sodium, is used in organic synthesis in the glass and chem-
ical industries. Both sodium and potassium ions are important in animal metabolism, but potassium ions
are far more important than sodium ions in plants and are therefore used extensively as fertilizers. The
normal daily intake from food is about 1.6 to 6.0 g. Daily natural potassium intake (1.6–6.0 g) con-
tributes to cardiovascular function, although excessive intake causes hyperkalemia, which may cause
cardiac arrest. Normal potassium levels in drinking water do not constitute a threat to human health.
Consequently, primary and secondary maximum contaminant levels (MCLs) are not available.
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Discussion of Metallic Elements 15
The physiological functions of sodium and potassium are essential in all living organisms. The
ions of these two elements do not create large and stable complexes with other organic molecules,
but they do function in ionic forms. Ion concentrations inside and outside cells are not in equilibrium
— potassium ion concentration is greater inside the cell, whereas sodium ions are more concentrated
outside the cell (see Figure 2.1). This asymmetric concentration is one of the most important energy
savers in living organisms and plays an important role in nerve stimulation and muscle function and
their physiological functions.
2.1.1.4 Rubidium (Rb) and Cesium (Cs)

Rubidium and cesium are rare and have little commercial importance. The name rubidium is derived
from the Latin rubidus, which means dark red. The name cesium derived from the Latin caesius,
which means sky blue. Cesium and rubidium were discovered by Bunsen and Kirchhoff in 1860 and
1861, respectively.
2.1.1.5 Francium (Fr)

Francium has a fleeting existence because all of its isotopes are radioactive and have a very short
half-life.
2.1.2 GROUP IIA (2): ALKALINE EARTH METALS

Alkaline earth metals are almost as reactive as the group IA metals; therefore, they always occur
in compounds. If we compare an alkaline earth metal with an alkali metal in the same period, the
FIGURE 2.1 Sodium–potassium exchange pump. The operation of this pump is an example of active trans-
port, because it depends on energy provided by ATP. For each ATP molecule converted to ADP, this ion pump
carries three Na+ ions out of the cell and two K+ ions into the cell.
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alkaline earth metal is less reactive and harder. For example, lithium is a soft metal, whereas beryl-
lium is hard enough to scratch. The most abundant alkaline earth metals are calcium and magne-
sium. The most common ions in seawater are Mg2+ and Ca2+. Marine organisms take calcium ions
from the water to make their calcium carbonate (CaCO3) shells. Underground brine also contains
a large concentration of these elements. These metals are found in mineral deposits in the Earth’s
crust, such as limestone (calcium carbonate, CaCO3) and dolomite (mixed calcium and magnesium
carbonate, CaCO3.MgCO3). Another important calcium mineral is gypsum (CaSO4.2H2O). Calcium
and magnesium are discussed in more detail later.
Like the alkali metals, certain alkaline earth metals give characteristic colors when added to a
flame. Calcium salts produce an orange-red color; strontium salts, bright red; and barium salts, yel-
low-green. These colors are intense enough to serve as flame tests. Like alkali metal salts, salts of
these metals are used in coloring fireworks displays.
2.1.2.1 Beryllium (Be)

Beryllium is found in the mineral beryl (Be3Al2(SiO3)6). Beryl minerals are emerald and aquama-
rine and, when cut and polished, they make beautiful gemstones. Beryllium is a very light metal
with excellent thermal conductivity and a high melting point, and most of its uses are based on these
properties. Because of its low density, excellent thermal conductivity, and elasticity, beryllium is
used in high-precision instruments. It is used to make x-ray tube windows, because it is the most
transparent mineral to x-rays. This metal is also used in alloys with copper and bronze to give them
hardness. Hammers and wrenches made from Be/Cu alloys do not produce sparks when struck
against steel and, therefore, can be used in flammable environments. Beryllium absorbs neutrons,
which are particles given off in nuclear reactions; consequently, it is used in nuclear power plants
and nuclear weapons.
Beryllium compounds are quite toxic, and some have become air pollutants due to combustion
emissions, cigarette smoke, and beryllium processing plants. Only its water-soluble salts (sulfates and
fluorides) have acute effects, causing dermatitis, conjunctivitis, and, through inhalation, irritation of
the respiratory tract. Chronic exposure to beryllium and its compounds may produce berylliosis, a fre-
quently fatal pulmonary granulomatosis. The toxic effect may be related to inhibition of enzyme ac-
tivities. There is a small quantity of beryllium in water source and soil. Because the concentration of
beryllium in water is minimal, it is not necessary to issue a public health standard.
2.1.2.2 Magnesium (Mg)

Magnesium is the lightest structural metal; its use is limited by its cost and flammability. The metal’s
name comes from the name of the mineral magnesite, which in turn is believed to stem from
Magnesia, a site in northern Greece where magnesium and other minerals have been mined since an-
cient times.
The British chemist Humphrey Davy discovered the pure element magnesium in 1808. He elec-
trolyzed a moist mixture of magnesium oxide and mercury(II) oxide, from which he obtained mag-
nesium amalgam (an alloy of magnesium dissolved in mercury). To obtain pure magnesium, he dis-
tilled off the mercury from the amalgam. Because magnesium has a very low density (1.74 g/cm3)
and moderate strength, it is useful as a structural metal when alloyed with aluminum. In flashbulbs,
a thin magnesium wire is heated electrically by a battery; the heat ignites the metal, which burns very
quickly in the pure oxygen atmosphere.
Magnesium is also used in antacids, the cathartic milk of magnesia (Mg(OH)2), and Epsom salts,
MgSO4.7H2O. Magnesium, together with calcium, contributes to water hardness. New users of
drinking water high in magnesium salts may initially experience a cathartic effect, but usually
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become tolerant. Magnesium is essential for neuromuscular conduction and is involved in many en-
zyme functions.
The major commercial sources of magnesium are seawater and minerals. It is nontoxic for hu-
mans, except in large doses. Magnesium does not constitute a public health hazard; before toxic lev-
els occur in drinking water, the taste cannot be tolerated.
2.1.2.3 Calcium (Ca)

Calcium is a common element that is present in the Earth’s crust as silicates, which weather to re-
lease a free calcium ion, Ca2+. The ion is about as abundant in seawater as the magnesium ion.
Corals are marine organisms that grow in colonies; their calcium carbonate (CaCO3) skeletons
eventually form enormous coral reefs in warm waters, such as the Bahamas and Florida Keys.
Deposits of limestone (mostly CaCO3) formed in earlier times as sediments of seashells and coral
and by the precipitation of CaCO3 from seawater.
Gypsum, hydrated calcium sulfate (CaSO4.2H2O), is another important mineral of calcium. When
heated moderately, it loses some water and the formula changes to (CaSO4)2.H2O or CaSO4.1/2H2O;
the water content changes to half of the original quantity. This partially dehydrated form of gypsum
is called plaster of Paris. (Early sources were mines in the Paris Basin, France.) When ground to a
fine powder and mixed with water to form a paste, it hardens within just a few minutes. This prop-
erty designated its uses, such as covering the interior walls of buildings, plasterboard, and plaster
casts. The fine-grained crystalline form of the mineral is called alabaster. It is a soft stone, easily
carved by sculptors; when highly polished, alabaster takes on a beautiful appearance. Calcium chlo-
ride (CaCl2) has a special high affinity to moisture. Calcium chloride can be purchased in hardware
stores for use in removing moisture from places with high humidity such as damp basements.
Calcium oxide (CaO) is among the top ten industrial chemicals. Calcium oxide is known com-
mercially as quicklime, or simply lime. Calcium oxide reacts exothermally with water to produce cal-
cium hydroxide (Ca(OH)2), commercially called slaked lime. Calcium hydroxide solutions react with
gaseous carbon dioxide (CO2,) to form calcium carbonate (CaCO3). An important use of this reaction
and the formation of the precipitated calcium carbonate is as a filler in the manufacture of paper. (The
purpose of the filler is to improve the paper’s characteristics, such as brightness and ink absorption.)
Large amounts of quicklime (CaO) and slaked lime (Ca(OH)2) are used to soften municipal water
supplies.
Numerous calcium compounds have therapeutic uses, such as antispasmodic, diuretic, and
antacid (e.g., Tums) preparations and treatment of low-calcium tetany. As discussed in Section 2.5.4,
calcium is essential for healthy bones and teeth. Hypercalcemia (excess calcium) occurs in vitamin
D poisoning in infants, hyperparathyroidism, sarcoidosis, and malignancy. Calcium toxicity can re-
sult in anorexia, nausea, vomiting, dehydration, lethargy, coma, and death. Excessive calcium levels
in drinking water may relate to the formation of kidney and bladder stones. Calcium concentration
in water is related to water hardness. High sodium and low calcium intake contributes to the devel-
opment of high blood pressure.
2.1.2.4 Strontium (Sr) and Barium (Ba)

Strontium and barium have few commercial uses as metals, other than as reducing agents in special-
ized metallurgical operations, and are thus produced in small quantities. One of the important uses
of barium sulfate (BaSO4) is in obtaining x-ray photographs of the digestive tract. A patient drinks a
suspension of barium sulfate in water and then the x-ray photograph is taken. The path of the patient’s
digestive tract is clearly visible on the film because BaSO4 is opaque to x-rays. Even though the
barium ion (Ba2+), like most heavy metal ions, is very toxic to humans, barium sulfate is safe, because
its solubility is so low and Ba2+ ions are barely absorbed by the body.
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Other uses of barium sulfate are based on its whiteness; it is used as a whitener in photographic
papers and as a filler in paper and polymeric fibers. The source of barium pollution is from mining
industries (coal), combustion (aviation and diesel fuel), and the mud resulting from oil well drilling.
Acute exposure to barium results in gastrointestinal, cardiac, and neuromuscular effects. Its maxi-
mum contaminant level (MCL) in drinking water is 5 mg/l.
2.1.3 GROUP IIIA (13) METALS

The Group IIIA elements clearly show the trend of increasing metallic characteristics when moving
downward in the column of elements in the periodic table. Boron (B), at the top of the column, is a met-
alloid, and its chemistry is typical of nonmetals. The rest of the elements in the column are metals.
2.1.3.1 Aluminum (Al)

Aluminum is the third most abundant element, and the most abundant metal in the Earth’s crust. It
occurs primarily in aluminum silicate minerals. The weathering of these rocks results in aluminum-
containing clay. Further weathering of the clay yields bauxite, the chief ore of aluminum. Bauxite
contains aluminum in the form of hydrated oxide (Al2O3.xH2O).
Aluminum always exists as the Al3+ ion. Aluminum has many uses, ranging from aluminum foil
to airplane construction. Its structural uses — building construction, electrical wiring and cables,
packaging and containers — are based on its low weight and moderate strength. Other interesting
uses of aluminum include drain cleaners, which consist mostly of NaOH along with small bits of alu-
minum metal. When sprinkled into a clogged drain, the bubbles caused by the release of hydrogen
gas cause a stirring effect in the clogged drain.
A thin layer of aluminum is used to reflect light in large visible-light telescopes. Dur-aluminum,
a solution of aluminum, manganese, and calcium, is used in the construction of buildings, boats, and
airplanes. Another alloy of aluminum is alnico, a mnemonic for aluminum, nickel, and cobalt.
Because the world supply of copper is diminishing, aluminum now replaces copper as the electrical
conductor in wires and cables. Pure aluminum, when heated in air at a high temperature, is totally
converted to aluminum oxide (Al2O3) or alumina. It is used as a carrier or support for many hetero-
geneous catalysts required for chemical processes, including those used in the production of gaso-
line. Aluminum oxide is used in the manufacture of ceramics. The word “ceramics” derives from the
Greek kerimikos, which means “of pottery,” referring to objects made by firing clay.
When aluminum oxide is fused (melted) at a high temperature, it forms corundum, one of the
hardest materials known. Corundum is used as an abrasive for grinding tools. The presence of impu-
rities results in various colors and produces gem-quality corundum. If the impurities in the corundum
structure are chromium oxides, then the crystal has a red color and is called ruby. Synthetic rubies,
for example, contain about 2.5% chromium oxide (Cr2O3). Ruby is used in fine instrument bearings
(jewel bearings) and in making lasers (see Appendix C). If the impurities are cobalt and titanium,
then the crystal is blue and it is called sapphire. If the impurities are iron oxides, the crystal is called
oriental topaz. Amethyst results when manganese oxide is the impurity in corundum.
When aluminum combines with iron(III) oxide, it releases a tremendous amount of energy, enough
that the resulting iron becomes molten. This reaction is known as the thermite reaction. Because tem-
peratures in excess of 3000°C are obtained, metals are welded using the thermite reaction.
Important aluminum compounds include aluminum hydroxide (Al(OH)3), which is an ingredient
in antacids. Potassium aluminum sulfate (KAl(SO4)2.12H2O), commonly called alum, is used as an ad-
ditive to neutralize base components of soils. Aluminum chloride (AlCl3) is frequently used as a cata-
lyst in laboratory syntheses and as an intermediate in a procedure for isolating aluminum from bauxite.
Aluminum sulfate (Al2(SO4)3) is used to make paper water resistant. Aluminum sulfate is also used in
water treatment plants, where it is added to the water along with lime (CaO). The CaO reacts with
L1572_C02 5/24/02 12:49 PM Page 19
water to make the solution alkaline. Gelatinous aluminum hydroxide will precipitate, thereby remov-
ing suspended solids and certain bacteria. Aluminum compounds are also used to prevent hyperphos-
phatemia in renal disease, and as antidotes. Until recently, aluminum was considered nontoxic.
Because Alzheimer’s disease patients have a high aluminum content in certain brain cells, research is
now focused on high aluminum intake as a possible causal factor. High aluminum intake originates
from packaging, aluminum cooking vessels, aluminum foil, and aluminum-containing antacids.
2.1.3.2 Gallium (Ga), Indium (In), and Thallium (Tl)

These metals have +1 and +3 oxidation states. Gallium has a melting point of only 29.8°C, so human
body temperature (37°C) is high enough to cause the metal to melt in the palm of your hand. Thallium
compounds are highly toxic; for humans, doses of 14 mg/kg and above are fatal. Thallium is used
mostly in electrical and electronic applications. Previously used in rodenticides, fungicides, and in
cosmetics, these products are now banned.
2.1.4 GROUP IVA (14) METALS

The two metallic elements in this column are tin (Sn) and lead (Pb). Both metals were known in
ancient times.
2.1.4.1 Tin (Sn)

Tin is a relatively rare element, ranking 50th or so in abundance in the Earth’s crust. The element oc-
curs in localized deposits of the tin ore cassiterite (SnO2). Sn refers to its original name, stannum.
Elemental tin occurs in three allotropic forms. The most common is called white tin, the shiny tin coat-
ing over steel. If tin is kept for long periods below 13.2°C, the white tin gradually changes to gray tin,
a powdery, nonmetallic form. Therefore, when tin objects are kept at low temperatures for long
periods, lumps develop on the surface. The phenomenon is called tin sickness or tin disease; histori-
cally, it was thought to be caused by an organism. For instance, during a cold winter in the 1850s, the
tin pipes of some church organs in Russia and other parts of Europe began crumbling from tin disease.
Tin disease is simply the transition from white tin to gray tin. The third allotropic form is brittle tin,
and its properties reflect its name. Tin is not found naturally in environmental samples; therefore, its
presence always indicates industrial pollution. The level of tin in drinking water systems is negligible.
Tin(IV) oxide (SnO2) is used to give glass a transparent, electricity-conducting surface. Bis-(trib-
utyltin)oxide is used in wood treatments to prevent rot. It has also been used in antifouling paints that
are applied to boat hulls to prevent the growth of marine organisms such as barnacles. However, its
high toxicity to all forms of marine life has led to a ban on its use for this purpose. Tin is used to make
tinplate, which is steel (iron alloy) sheeting with a thin coating of tin. Tinplate is used for food con-
tainers (“tin cans”). Tin(II) chloride (SnCl2) is used as a reducing agent in the preparation of dyes and
other organic compounds. An excellent reducing agent, SnCl2 is used in the preparation of dyes and
other organic compounds. Tin(IV) chloride (SnCl4) is a liquid; it freezes at −33°C. A tin coating pro-
tects iron from reacting with air and food acids. Tin is also used to make numerous alloys, including
solder, a low-melting alloy of tin and lead, and bronze, an alloy of copper and tin.
2.1.4.2 Lead (Pb)

Lead occurs in the form of lead sulfide (PbS), known as galena. The Latin word for lead is plumbum,
thus its symbol, Pb. The word “plumber” comes from the early use of lead water pipes and pipe joints.
Lead is a very heavy, soft, highly malleable, bluish-gray metal and exists in +2 and +4 oxidation
states, although lead(II) compounds are the more common.
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In lead storage batteries, the cathode is lead(II) oxide (PbO, called litharge), which is packed into
a lead metal grid (PbO is a reddish-yellow solid). When the battery is charged, the PbO is oxidized to
lead(IV) oxide (PbO2 is a dark brown powder). The metal is used to make batteries and solder and to
manufacture tetraethyllead ((C2H5)4Pb), a gasoline octane booster. The use of lead-containing additives
in gasoline has been phased out in many countries (but not all) because of environmental hazards.
Lead is toxic to the nervous system and children are especially susceptible to its effects. It is read-
ily absorbed from the intestinal tract and deposited in the central nervous system. The first lead water
pipes were used in ancient Rome by upper-class citizens; their children drank the water throughout
childhood and thus were at high risk of lead toxicity. This fact may explain the bizarre behavior of
certain notorious Roman emperors and the fall of the Roman Empire. In recent years, exposure to
lead toxicity has become widespread. Sources are lead-containing paint, air, soil, dust, food, and
drinking water. The presence of lead in the body is indicated by lead blood levels, expressed as mi-
crograms of lead per deciliter of blood (µg/dl). Blood lead levels of 10 µg/dl and higher may con-
tribute to learning disabilities, nervous system damage, and stunted growth. Many children suffered
lead poisoning from ingestion of lead-based paints. Lead-based paint was used inside many homes
until Congress passed the Lead-Poisoning Prevention Act in 1971. Lead is encountered in air, soil,
and water. The concentration of lead in natural waters has been reported to be as high as 0.4 to 0.8
mg/l, mostly from natural sources, such as galena deposits. High contamination levels may be caused
by industrial and mining pollution sources. High levels of lead in drinking water are mostly the re-
sult of corrosion products from lead service pipes, solders, and household plumbing. According to a
survey by the Environmental Protection Agency, infants dependent on formula may receive more
than 85% of their blood lead levels from drinking water. Lead as a corrosion product in drinking
water is associated with copper. Copper is needed for good health, and in low levels it has a benefi-
cial effect, but in high concentrations it is toxic, causing diarrhea and vomiting. The maximum con-
taminant level (MCL) established for lead in drinking water is 0.02 mg/l, but the maximum contam-
inant level goal (MCLG) for lead is zero, and for copper, 1.3 mg/l.
2.1.5 GROUP VA (15) METALS

2.1.5.1 Bismuth (Bi)
The only metallic element in group VA is bismuth. It is one of the few substances that expand slightly
at freezing. This property makes bismuth ideal to use for castings because it expands to fill all details
of the mold. The other principal use of bismuth is in making alloys with unusually low melting points.
For example, Wood’s metal, an alloy, contains 50% bismuth, 25% lead, 12.5% tin, and 12.5% cad-
mium. The alloy melts when dipped into boiling water (melting point is 70°C).
2.2 TRANSITION METALS

2.2.1 GENERAL DISCUSSION
The transition elements or metals are elements normally placed in the body of the periodic table, the
B groups. The inner transition elements are located in the long row, usually found just below the main
body of the table. Elements in the first row are called lanthanides because they follow lanthanum.
Elements in the second row are called actinides because they follow actinium. The lanthanides and
actinides are rare elements (see Sections 1.2 and 2.2.2).
Many of the transition elements have properties in common. One of the most important charac-
teristics of the transition metals is the occurrence of multiple oxidation states. The oxidation state of
the metal is expressed by using special nomenclature for these elements. In the stock system, the full
name of the metal is followed by its oxidation number (valence) in Roman numerals enclosed in
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parentheses. The old nomenclature system assigned names to metals in a different way. The ending
“-ic” designates the higher oxidation states, while “-ous” identifies the lower oxidation state of the
metal. The names of metals with multiple oxidation states are listed in Table 2.1.
Another property of transition elements is the tendency of ions to combine with neutral mole-
cules or anions to form complex ions, or chelates. The number of complexes formed by the transition
metals is enormous, and their study is a major part of chemistry. (Chelate formation and its impor-
tance in medicine are discussed in Section 3.2.) Many compounds and complexes of the transition
metals have beautiful colors, because the transition metal in the complex ion can absorb visible light
of specific wavelengths. For instance, all chromium compounds are colored; in fact, chromium gets
its name from the Greek chroma, which means color.
Many of the atoms and ions of the transition elements contain unpaired electrons. Substances
with unpaired electrons are attracted to a magnetic field and are said to be paramagnetic. The attrac-
tion tends to be weak, however, because the constant movement and collision between the individual
atomic-sized magnets prevent large numbers of them from becoming aligned with the external mag-
netic field. The magnetic property we often associate with iron is its strong attraction to the magnetic
field. In reality, iron is one of three elements (iron, cobalt, and nickel) that exhibit this strong mag-
netism, called ferromagnetism. Ferromagnetism is about 1 million times stronger than paramagnet-
ism. Ferromagnetism is a property specific to the solid state. Alloys with ferromagnetic properties
have been manufactured, such as alnico magnets — alloys of iron, aluminum, nickel, and cobalt.
Manganese is paramagnetic, but by adding copper to manganese a ferromagnetic alloy is formed.
Transition metals have many uses. For instance, iron is used for steel; copper for electrical wiring
and water pipes; titanium for paint; silver for photographic paper; manganese, chromium, vanadium,
and cobalt as additives to steel; and platinum for industrial and automotive catalysts. Transition metal
ions also play a vital role in living organisms. For example, iron complexes provide the transport and
storage of oxygen, molybdenum and iron compounds are catalysts in nitrogen fixation, zinc is found
TABLE 2.1
Metals with Multiple Oxidation States
Metal Oxidation Stock Name Old Name
Copper +1 Copper(I) Cuprous
+2 Copper(II) Cupric
Mercury +1 Mercury(I) Mercurous
+2 Mercury(II) Mercuric
Iron +2 Iron(I) Ferrous
+3 Iron(III) Ferric
Chromium +2 Chromium(II) Chromous
+3 Chromium(III) Chromic
Manganese +2 Manganese(II)
Manganous
+3 Manganese(III) Manganic
Cobalt +2 Cobalt(II) Cobaltous
+3 Cobalt(III) Cobaltic
Tin +2 Tin(II) Stannous
+4 Tin(IV) Stannic
Lead +2 Lead(II) Plumbous
+4 Lead(IV) Plumbic
Titanium +3 Titanium(III) Titanous
+4 Titanium(IV) Titanic
Note: Mercury(I) is a diatomic molecule; that is, it exists in pairs as Hg22+. Whatever the notation
style of mercury(I), it indicates a pair of mercury ions.
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in more than 150 biomolecules in humans, copper and iron play a crucial role in the respiratory cycle,
and cobalt is found in essential biomolecules such as vitamin B12.
The transition metals behave as typical metals, possessing metallic luster and relatively high
electrical and thermal conductivities. Silver is the best conductor of heat and electrical current.
However, copper is a close second, which explains copper’s wide use in electrical systems. In spite
of these metals’ many similarities, their properties vary considerably. For example, tungsten has a
melting point of 3400°C and is used for filaments in light bulbs, and mercury is a liquid at 25°C.
Some transition metals, such as iron and titanium, are hard and strong and are thus very useful struc-
tural materials. Others, such as copper, gold, and silver, are relatively soft. Chemical properties also
vary significantly. Some react readily with oxygen to form oxides. These metals, such as chromium,
nickel, and cobalt, form oxides that adhere tightly to the metallic surface, protecting the metal from
further oxidation. Others, such as iron, form oxides that scale off, exposing the metal to further cor-
rosion. Noble metals, such as gold, silver, platinum, and palladium, do not form oxides. An intro-
duction to some of these important metals and their specific properties follows.
2.2.1.1 Scandium (Sc)

Scandium’s atomic number is 21. Scandium is a rare element that exists in compounds, mainly in the
+3 oxidation state. This metal is not widely used because of its rarity, high reactivity, and high cost.
It is found in some electronic devices, such as high-density lamps.
2.2.1.2 Titanium (Ti)

Titanium is widely distributed in the Earth’s crust. Because of its relatively low density and high
strength, titanium is an excellent structural material, especially in jet engines where light weight and
stability at high temperatures are required. It is used also in manufacturing racing bicycles. Its re-
sistance to chemical reactions makes it useful material for pipes, pumps, and reaction vessels in the
chemical industry. Titanium(IV) oxide (TiO2) is used as the white pigment in papers, paints, linoleum,
plastics, synthetic fibers, and cosmetics. Titanium is found in several minerals; one of the most im-
portant is rutile (TiO2). Titanium tetrachloride (TiCl4) is a clear, colorless, volatile liquid with a boil-
ing point of only 136°C and whose vapors react almost instantly with moist air to form a dense smoke
of TiO2. The reaction was once used by the U.S. Navy to create smoke screens during naval battles.
2.2.1.3 Vanadium (V)

Vanadium is widely spread in the Earth’s crust. A gray, relatively soft metal, it is found in various
minerals. It is used mostly in alloys with other metals, such as vanadium steel (80% vanadium), a
hard steel used in engine parts and axles. Vanadium(V) oxide, (V2O5, vanadium pentoxide), is used as
an industrial catalyst. Vanadium salts have low oral toxicity and medium toxicity via inhalation.
Vanadium is possibly a protective agent against atherosclerosis.
2.2.1.4 Chromium (Cr)

Although very rare, chromium is a very important industrial metal. It is a grayish-white crys-
talline, very hard metal, with high resistance to corrosion. Chromium maintains a bright surface
by developing a tough invisible oxide coating. These properties make it an excellent decorative
and protective coating for other metals, such as brass, bronze, and steel. Chrome plate is de-
posited electrolytically on automobile parts such as bumpers.
Large amounts of chromium are used to produce alloys, such as stainless steel, which contains
about 18% chromium, 8% nickel, and small amounts of manganese, carbon, phosphorus, sulfur and
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silicon, all combined with iron. Nichrome, an alloy of chromium and nickel, is often used as a wire-
heating element in devices such as toasters.
The many colorful compounds of this element are a fascinating feature of chromium chemistry.
The common oxidation states of chromium compounds are +2, +3, and +6. The color of the
chromium(III) species depends on anions in solution that can form complexes with Cr3. The ion is
frequently green. Chromium(VI) oxide (CrO3, also called chromium trioxide), is a red crystalline
compound. It precipitates when concentrated sulfuric acid is added to concentrated solutions of a
dichromate salt. Red chromium(VI) oxide (CrO3) dissolves in water to give a strong, acidic, red-or-
ange solution; when made basic, the solution turns yellow. CrO3, the anhydride of chromic acid
(H2CrO4), is a highly poisonous red-orange compound. At a higher pH, two other forms predominate,
the yellow chromate ion (CrO42–) and the red-orange dichromate ion (Cr2O72–).
A mixture of chromium(VI) oxide and concentrated sulfuric acid, commonly called cleaning so-
lution, is a powerful oxidizing medium that can remove organic materials from analytical glassware,
yielding a very clean surface. Commercial substitutes for dichromate-sulfuric acid, such as
Nichromix, do not contain chromium and hence are safer to use. One of the principal uses of
chromium compounds is in pigments for coloring paints, cements, and plasters. The Cr2+ ion is a pow-
erful reducing agent in aqueous solution; therefore, it is used to remove traces of oxygen from other
gases by bubbling through a Cr2+ solution. The Cr6+ ions are excellent oxidizing agents. Zinc yellow
pigment (ZnCrO4, zinc chromate) is used as a corrosion inhibitor on aluminum and magnesium air-
craft parts. Cr3+ (trivalent) chromium may be essential in human nutrition, but Cr6+ (hexavalent) is
highly toxic. Among other health problems, intake of hexavalent chromium can cause hemorrhaging
in the liver, kidneys, and respiratory organs. Workers exposed to hexavalent chromium have devel-
oped dermatitis and ulceration and perforation of the nasal septum. Gastric cancers, presumably from
excessive inhalation of dust containing chromium, have also been reported.
2.2.1.5 Manganese (Mn)

Manganese is found in many minerals as oxides, silicates, and carbonates. One interesting source of
manganese is manganese nodules found in the ocean floor. These roughly spherical “rocks” contain
a mixture of manganese and iron oxides as well as smaller amounts of other metals, such as cobalt,
nickel, and copper. Apparently the nodules were formed at least partly from the action of marine or-
ganisms (see Section 1.5).
Manganese is a very brittle metallic element resembling iron, but harder, and is complicated by
the existence of six oxidation states from +1 to + 7, although +2 and +7 are the most common.
Manganese(II) forms an extensive series of salts with all of the common anions. Manganese(VII) is
found in the purple-colored permanganate ion (MnO4–). Manganese is principally used in iron alloys,
dry cells, and oxidizing chemicals, as potassium permanganate (KMnO4). The metal is also used as
a steel additive and in the preparation of other alloys, such as manganese bronze (a copper–
manganese alloy) and manganin (an alloy of copper, manganese, and nickel, whose electrical resist-
ance changes slightly with temperature).
Manganese toxicity to humans has been shown only on exposure to high levels in the air.
Inhalation of large doses of manganese compounds, especially the higher oxides, can be lethal.
Inhalation of manganese fumes causes manganese pneumonia, which can be fatal. Chronic man-
ganese toxicity is well known in miners, mill workers, and others exposed to high concentrations of
manganese-laden dust and fumes, and drinkers of well water containing excessive manganese (often
in mining villages). The usual symptoms involve the central nervous system. Characteristic man-
ganese psychosis involves inappropriate laughter, euphoria, impulsiveness, and insomnia, followed
by overwhelming somnolence. These symptoms may be accompanied by headache, leg cramps, and
sexual excitement, followed by lethargy. In the final stage, speech disturbance, masklike facial
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expression, general clumsiness, and micrography (very minute writing) are characteristic. Although
patients may become totally disabled, the syndrome is not lethal.
2.2.1.6 Iron (Fe)

Iron is the most abundant heavy metal. Its chief ores are the red-orange hematite (Fe2O3) and the black
magnetite (Fe3O4). Iron contains both the +2 and +3 oxidation states. Iron and its carbon alloy, steel,
constitute the backbone of modern industrial society. It is a white, lustrous, not particularly hard metal
that is very reactive toward oxidizing agents. For example, in moist air iron is rapidly oxidized to form
rust, a hydrated oxide, whose formula is usually given as Fe2O3.xH2O (Figure 2.2). Rust does not ad-
here well to the metal, but instead falls away, exposing fresh iron to attack. One way to prevent rusting
is to coat the iron with another metal such as tin. Another way to prevent corrosion is called cathodic
protection, which involves placing the iron in contact with another metal that is more easily oxidized.
This causes iron to react as a cathode (the electrode at which reduction occurs during an electrochemi-
cal change) and the other metal to be the anode (the electrode at which oxidation occurs during an elec-
trochemical change). If corrosion occurs, the iron is protected from oxidation because it is cathodic and
the other metal reacts instead. Zinc is most often used to provide cathodic protection to other metals.
Corrosion protection is illustrated in Figure 2.3. Steel objects that must withstand weather are
often coated with a layer of zinc, a process called galvanizing. Iron is also quite reactive to nonox-
idizing acids, such as hydrochloric acid (HCl) and sulfuric acid (H2SO4). Iron does not react with
concentrated nitric acid (HNO3). Instead, because its surface becomes quite unreactive, the iron is
said to have been made passive. The chemistry of iron mainly involves its +2 and +3 oxidation
states. Iron(II) salts are generally light green, and iron(III) salt solutions usually range from yel-
low to brown.
Iron ions form many complex ions. Iron is the central metal in the hemoglobin molecule, and iron
is used in the therapy of iron-deficiency anemia. Iron and its compounds are used as pigments, mag-
netic tapes, catalysts, disinfectants, tanning solutions, and fuel additives. Iron is an essential mineral,
but toxic in high doses.
Iron content of environmental samples is mostly attributed to feeding aquifers, corrosion from
pipes, leachate from acid mine drainage, and iron-product industrial wastes. Ferrous (Fe2+) and fer-
ric (Fe3+) iron are soluble in water, but ferrous iron is easily oxidized to ferric hydroxide, which is not
soluble in water and thus flocculates and settles. High iron concentration in water can cause staining
of laundry and porcelain and a bittersweet astringent taste. To prevent the formation of black iron
Water drop
O2 O2
OH – Fe2+ OH –
Cathode Rust Rust Cathode
Anode
Iron
FIGURE 2.2 Electrochemical process involved in rusting of iron. Shown here is a single drop of water con-
taining ions from a voltaic cell in which iron is oxidized to an iron(II) ion at the center of the drop. Hydroxide
ions and iron(II) ions migrate together and react to form iron(II) hydroxide. Iron(II) hydroxide is oxidized to
iron(III) hydroxide by more O2 that dissolves at the surface of the drop. Iron(III) hydroxide precipitates and set-
tles to form rust on the surface of the iron.
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FIGURE 2.3 Rust prevention: cathodic protection of a buried steel pipe. Iron in the steel becomes the cathode
in an iron–magnesium voltaic cell. Magnesium rather than iron is oxidized.
deposits and iron bacterial growth, oxygen in the water should be higher than 2 mg/l and the free-
chlorine residual concentration should be higher than 0.2 mg/l. Maintaining a pH above 7.2 in the
distribution system also helps to avoid high levels of iron deposition.
2.2.1.7 Cobalt (Co)

Cobalt is relatively rare and is found in ores such as smaltite (CoAs2) and cobaltite (CoAsS). Cobalt
is a hard, bluish-white metal that is used mainly in alloys, such as stainless steel and stellite (an alloy
of iron, copper, and tungsten), which is used in surgical instruments. Cobalt is also used to prepare the
alloy alnico, which forms powerful magnets. Aqueous solutions of cobalt(II) salts are characteristi-
cally rose colored. Cobalt salts, the usual oxidation states II and III, are used to give a brilliant blue
color to glass, tiles, and pottery. Anhydrous cobalt(II) chloride (CoCl2) is used in water quality testing
and as a heat-sensitive ink. Artificially produced cobalt-60 is used as a radioactive tracer and cancer
treatment agent. Cobalt is a part of vitamin B12 (cyanocobalamin) and is considered an essential nu-
trient, but concentrations higher than 1 mg/kg of body weight are regarded as a health hazard. The for-
mula for vitamin B12 appears in Figure 2.4. Cobalt exhibits toxic effects on the heart, kidneys, and thy-
roid gland. Consumption of large quantities of coffee or beer may lead to high concentrations of
cobalt. Cobalt toxicity resulting in heart failure (about 40% mortality) has been reported among heavy
beer drinkers who had consumed products containing cobalt additives used as a foam stabilizer.
2.2.1.8 Nickel (Ni)

This element ranks 24th in abundance in the Earth’s crust. Nickel metal is a silver-white, malleable,
ductile substance with high electric and thermal conductivity. Because it is quite resistant to corro-
sion, nickel is often used in plating more active metals. Nickel and chromium are the chief additives
to iron in making stainless steel. Combined with copper, nickel produces a hard, strong, corrosion-
resistant alloy called monel. Because boats operate in the corrosive environment of seawater, monel
is used in the manufacture of boat propeller shafts.
Nickel is also used as a catalyst for the hydrogenation of organic compounds that contain double
bonds. Nickel in compounds is almost exclusively in the +2 oxidation state. Aqueous solutions of
nickel(II) salts have a characteristic emerald-green color. Nickel and its compounds have little toxi-
city. Nickel itch or contact dermatitis is the most commonly seen reaction to nickel compounds,
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FIGURE 2.4 Formula of vitamin B12.
especially in women, resulting from use of nickel in costume jewelry, especially earrings. Chronic
exposure to nickel causes cancer in the respiratory tract and the lungs.
2.2.1.9 Copper, Silver, and Gold

Copper, silver, and gold are often called the “coinage metals” because they have been used for that
purpose since ancient times. They can be found in nature as free metals, a reflection of their stability.
Copper (Cu) is widely distributed in nature in ores containing sulfides, arsenides, chlorides, and
carbonates. A reddish-brown, malleable, ductile metal, copper is valued for its high electrical con-
ductivity and resistance to corrosion. It is used in plumbing and electrical applications. The reddish-
colored metal oxidizes slowly in air; when CO2 is also present, its surface becomes coated with a
green film of Cu2(OH)2CO3. The outer surface of the Statue of Liberty is made of copper, and this
compound gives the statue its green color. Copper has long been used in the United States to make
pennies, but since 1981 new pennies have been made from zinc with a thin copper coating. Copper
principally exists in the +2 oxidation state, but compounds containing copper(I) ion are also known.
Copper(II) oxide (CuO) is black, and copper(I) oxide (Cu2O) is red. Usually, copper(II) compounds
have a characteristic bright blue color.
Although trace amounts of copper are essential for life, copper in large amounts is quite toxic.
For example, copper salts are used to kill bacteria, fungi, and algae, and paints containing copper are
used on ship hulls to prevent fouling by marine organisms. Copper is essential to human nutrition be-
cause it plays a major role in enzyme functions.
Silver (Ag) has the highest thermal and electrical conductivity of any metal. Its value as a
coinage metal, however, makes it too expensive to be used often as an electrical conductor. Silver has
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a high luster, and, when polished, reflects light very well. This makes it valuable for jewelry and for
the reflective coating on mirrors. Silver is soft and usually alloyed with copper. Sterling silver, for
example, contains 7.5% copper, and silver used for jewelry often contains as much as 20% copper.
Silver is even more difficult to oxidize than copper. Metallic silver is not attacked by oxygen in the
air, but it does tarnish in air by reacting with oxygen and traces of hydrogen sulfide, H2S (formed in
nature by decomposing vegetation). The black tarnish deposit is silver sulfide (Ag2S). Similar reac-
tions occur if silver utensils are left in contact with sulfur-containing foods, such as eggs and mus-
tard.
One of silver’s most important applications is in photography. Silver salts tend to be unstable and
sensitive to light. Silver iodide is used to “seed” clouds to bring on rain. The most important oxida-
tion state of silver is +1.
The major problem in humans arising from overexposure to silver is called argyria, which is
characterized by blue-gray coloration of the skin, mucous membranes, and internal organs.
According to a report by the World Health Organization in 1987, a continuous daily dose of 0.4 mg
of silver intake may produce argyria.
Gold (Au) is valuable as bullion and as a decorative metal in jewelry and other artifacts. This el-
ement is also used occasionally to plate electrical contacts because of its low chemical reactivity.
Pure gold is very soft and it is particularly ductile and malleable. Gold leaf is made by pounding gold
into very thin sheets. Gold is so unreactive that even concentrated nitric acid (HNO3) fails to attack
it. A special solution, called aqua regia, dissolves gold slowly. (Aqua regia consists of one part con-
centrated HNO3 and three parts concentrated HCl.) Gold is found as a free element in nature because
its compounds are so unstable.
2.2.1.10 Zinc (Zn)

This metal is mainly refined from sphalerite ((ZnFe)S), which often occurs in galena (PbS). Zinc is
a white, lustrous, very active metal that behaves as an excellent reducing agent and tarnishes rapidly.
Because of zinc’s excellent reactivity, its surface quickly acquires a film of a basic carbonate,
Zn2(OH)2CO3; this coating protects the metal below from further oxidation. About 90% of the zinc
produced is used for galvanizing steel. (See detailed discussion of galvanization and cathodic pro-
tection against corrosion in Section 2.2.1.6.) The automotive industry has used galvanized steel to
make rustproof automobile bodies.
Zinc exists in the +2 oxidation state, and its salts are colorless. Zinc compounds are used in many
applications. Zinc oxide (ZnO), a white powder, is used in various creams, such as sunscreens, and
to make quick-setting dental cements. Zinc sulfide (ZnS) can be used to prepare phosphor substances
that glow when bathed in ultraviolet light or the high-energy electrons of cathode rays. Such phos-
phors are used on the inner surface of television picture tubes and the CRT displays of computer mon-
itors and in devices for detecting atomic radiation. Zinc is also used in dry batteries.
Zinc is an essential trace element in human nutrition. High concentrations of zinc are found in
the male reproduction system, muscles, kidneys, liver, pancreas, and the thyroid and other endocrine
glands. Zinc is also an important component of enzymes. Excessive zinc intake may inhibit copper
absorption and lead to copper deficiency. Acidic beverages packaged in galvanized containers may
produce toxic zinc concentration levels, causing nausea, vomiting, stomach cramps, and diarrhea.
2.2.1.11 Yttrium (Y)

The yttrium metals include terbium (Te), a lanthanide (at. no. 65); erbium (Er), another lanthanide
(at. no. 68); ytterbium (Yb), yet another lanthanide (at. no. 70); and yttrium (Y), a transition metal
(at. no. 39). These metals are all related to ores found in Ytterby, a small town near Stockholm.
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Yttrium–aluminum garnets (Y3Al2O15), commonly referred as YAGs, are used in lasers (see Appendix
C) and electronic equipment (microwave filters) and as synthetic gems.
2.2.1.12 Zirconium (Zr) and Hafnium (Hf)

Zirconium and hafnium occur together in nature because their ions are the same size and have the
same charge. These similarities make it difficult to separate them from each other.
Zirconium and zirconium oxide (ZrO) are highly resistant to high temperatures. Their primary
use has been in spacecraft that must reenter the atmosphere. Hafnium is named after the Latin term
for Copenhagen. This element was originally found in samples that had been mistakenly identified
as pure zirconium, as well as in zirconium ores.
2.2.1.13 Niobium (Nb) and Tantalum (Ta)

Niobium and tantalum were “tantalizingly” difficult to separate, and thus named after the mytholog-
ical Tantalus and his daughter Niobe. Both are transition elements, with the atomic numbers of 41
and 73, respectively. Niobium steel is used in atomic reactors because it has sufficient strength to han-
dle high temperatures over long periods of time.
2.2.1.14 Molybdenum (Mo)

Molybdenum is a lustrous, silver-white, metallic element, mostly used in alloys, and is particularly
valuable in enhancing the quality of stainless steel. Molybdenum is also used in nuclear energy pro-
duction, electrical products, and glass and ceramics. Molybdenum is an essential trace mineral in the
meats of ruminants and in plants. Deficiencies are unknown in humans; apparently practically any
diet supplies sufficient amounts to carry out this element’s roles in enzyme functions.
2.2.1.15 Tungsten (W)

This symbol refers to its Latin name, wolframate. The metal is prepared from tungsten(VI) oxide, a
canary-yellow compound obtained from the processing of tungsten ore. One of the most important
uses of tungsten metal is the production of filaments for incandescent light bulbs. This usage depends
on the fact that tungsten has the highest melting point (3410°C) and highest boiling point (5900°C)
of any metal. To be useful, the incandescent filament in a light bulb must not melt and should not va-
porize excessively. The tungsten metal filament does slowly vaporize, and the condensed metal often
appears as a black coating on the inside surface of a burned-out bulb. In a light bulb, a coiled wire of
tungsten becomes white hot when an electric current flows through it. The wire is enclosed in a glass
bulb containing gases that do not react with the tungsten, such as nitrogen and argon. The gases carry
the heat away from the wire, which would otherwise overheat and boil away.
Cobalt, chromium, and tungsten form the alloy stellite, which retains its hardness even when hot.
This characteristic makes stellite useful for high-speed cutting tools used to machine steel. In inter-
stitial carbides, carbon atoms occupy spaces or interstices within the lattice of metal atoms, which
results in a material with many characteristics of a metal, such as conductivity and luster. An indus-
trial example is tungsten carbide (WC), which is used to make high-speed cutting tools because it is
exceptionally hard and chemically stable even as the tool becomes very hot during use.
2.2.1.16 Technetium (Tc)

Technetium is a transition metal with an atomic number of 43. It has no isotopes. The nucleus of
every technetium isotope is radioactive and decays or disintegrates, producing an isotope of another
element. Because of its nuclear instability, technetium is not found naturally on Earth. Nevertheless,
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it is produced commercially in kilogram quantities from other elements by nuclear fission, a process
in which nuclei are transformed. Technetium derives its name from the Greek word tekhnetos, mean-
ing artificial. Technetium was the first new element produced in the laboratory from another element.
It was discovered in 1938 by Carlo Pierrer and Emilio Segre when the element molybdenum was
bombarded with deuterons (nuclei of hydrogen, each consisting of one proton and one neutron).
Technetium is one of the principal isotopes used in medical diagnostics based on radioactivity. A
compound of technetium is injected into a vein, where it concentrates in certain organs. The energy
emitted by technetium nuclei is detected by special equipment and provides an image of the organs.
2.2.1.17 Ruthenium (Ru), Osmium (Os), Rhodium (Rh), Iridium (Ir),

Palladium (Pd), and Platinum (Pt)
These metals are collectively known as platinum metals. The six elements following technetium
(Tc), element 43, and rhenium (Re), element 75, are similar and occur together in various combi-
nations in nature.
2.2.1.18 Cadmium (Cd)

Cadmium is less abundant than zinc and is usually found as an impurity in zinc ores. The free metal
is soft and moderately active. Its chief use is as a protective coating on other metals, including met-
als exposed to an alkaline environment, and for making nickel-cadmium batteries.
Cadmium compounds are quite toxic; if absorbed by the body they can cause high blood pres-
sure, heart disease, and even death. Acute overexposure to cadmium fumes may cause pulmonary
damage, while chronic exposure is associated with renal tube damage and an increased risk of
prostate cancer. The high level of cadmium in cigarette smoke contributes to air pollution. Cadmium
may contaminate water supplies from mining, industrial operations, and leachate from landfill. It also
may enter water distribution systems through corrosion of galvanized pipes.
2.2.1.19 Mercury (Hg)

Mercury is a heavy, silver-white liquid metal. Its symbol corresponds to the Latin hydrargyrum,
which means quick silver. Its chief ore is cinnabar or mercury sulfide (HgS). Mercury is liquid at
room temperature; it freezes at −38.9°C and boils at 357°C. This large and convenient liquid tem-
perature range accounts for mercury’s use as the fluid in thermometers. A useful property of mercury
is its ability to dissolve many other metals to form solutions called amalgams. A silver amalgam used
in teeth fillings for many years is no longer used because of the highly toxic effects of mercury.
Mercury is a less-active metal than zinc or cadmium. In compounds, mercury occurs in two ox-
idation states, +1 and +2. Mercury(I) chloride (Hg2Cl2), also known as calomel, is very insoluble in
water. Its low solubility permitted its uses as an antiseptic and treatment for syphilis before the dis-
covery of penicillin. The body retains very little mercury because so little Hg2Cl2 is able to dissolve.
Mercury(II) chloride (HgCl2) is water soluble and highly poisonous. The addition of H2S to a so-
lution containing mercury(II) chloride produces a black precipitate of HgS. When heated, its crystal
structure changes and becomes a brilliant red substance, called vermilion.
Because mercury is absorbed by lung tissue, mercury vapor is hazardous, especially when
heated. Mercury is a nervous system toxin, causing tremors, ataxia (uncoordinated muscle move-
ments), irritability, slurred speech, psychiatric disorders, blindness, and death. (Thus, when ther-
mometers break inside infant incubators, the spilled mercury vapor can leak into the heating unit,
causing a severe hazard to infants.) Mercuric nitrate (Hg(NO3)2) was once used in the manufacture
of felt for hats. Workers often developed severe mercury poisoning, an affliction that leads to cen-
tral nervous system disorders, loss of hair and teeth, loss of memory, and tremors or “hatter’s
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shakes” (hence the term, “mad as a hatter”). In the 1950s, an outbreak of mercury poisoning from
contaminated seafood in Minamata Bay, Japan, raised awareness of the mercury hazard. The main
sources of mercury pollution are industrial wastes and incinerators, power plants, laboratories, and
even hospitals.
In streams and lakes, inorganic mercury is converted by bacteria into two organic forms: dimethyl
mercury and methyl mercury. Dimethyl mercury is very volatile and evaporates quickly, but methyl
mercury remains in the bottom sediment and is slowly released into the water, where it enters or-
ganisms in the food chain and is biologically magnified. Freshwater fish are particularly at risk, es-
pecially near paper plants where mercuric chloride (HgCl2) is used as a bleach for paper and then dis-
charged into the water. Organic mercury compounds continue to be used as fungicides in seeds for
crop planting.
2.2.2 INNER TRANSITION ELEMENTS

2.2.2.1 Lanthanides
The elements from lanthanum (La, at. no. 57) through lutetium (Lu, at. no. 71) are collectively called
the lanthanides, or the rare earth elements. To the ancient Greeks, metal oxides were known as
“earths.” Because these elements were first found in rare minerals as oxides, they became known as
the rare earth elements. Although often difficult to isolate, many of the rare earth metals are not par-
ticularly rare. Cerium (Ce, at. no. 58) is the most abundant rare earth element; thulium (Tm, at. no.
69) and promethium (Pm, at. no. 61) are the least abundant.
All lanthanides are shiny, silvery, reactive elements. Most readily tarnish in air by the formation
of oxides, although gadolinium (Gd, at. no. 64) and lutetium (Lu, at. no. 71) are quite stable. Some
form white oxides and colorless ions in aqueous solutions, while others have colored ions and ox-
ides. The pure metals range in density from 6.2 g/cm3 for lanthanum to 9.8 g/cm3 for lutetium, and
their melting points all fall between about 800 and 1600°C. The principal use of lanthanide com-
pounds is in petroleum-cracking catalysts. The glass and metallurgy industries also consume lan-
thanide compounds. In some alloys, rare earths are used to impart desirable properties and in others
to react with sand to remove undesirable impurities.
Praseodymium (Pr, at. no. 59) and neodymium (Nd, at. no. 60) are added to the glass in welders’
goggles to absorb the bright yellow light of the sodium flame. Cerium oxide is effective in polishing
camera and eyeglass lenses. Pure neodymium oxide is added to glass to produce a beautiful purple
color. A mixed oxide of europium and yttrium (Eu2O3 and Y2O3) produces a brilliant red phosphor that
is used in color television screens. To mention just one more application of a lanthanide, yttrium–
aluminum garnets (YAGs) are used in electronic equipment (e.g., microwave filters) and as synthetic
gems.
2.2.2.2 Actinides
The elements from actinium (Ac, at. no. 89) through lawrencium (Lr, at. no. 103) are collectively
called the actinides. All actinides are radioactive.
Elements with atomic numbers greater than 92 (the at. no. of uranium is 92) are called the
transuranium elements, the naturally occurring elements of greatest atomic number. In 1940, E.M.
McMillan and P.H. Abelson, at the University of California, Berkeley, discovered the first transura-
nium element. They produced an isotope of element 93, which they named neptunium. The next
transuranium element to be discovered was plutonium (at. no. 94). The next two transuranium ele-
ments were americium (at no. 95) and curium (at. no. 96). Transuranium elements have a number of
commercial uses. For instance, plutonium-238 isotope has been used as a power source for space
satellites, navigation buoys, and heart pacemakers. Americium-241 is used in home smoke detectors.
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2.3 METALLOIDS
2.3.1 GROUP IVA (14)
2.3.1.1 Silicon (Si)
Silicon is a representative metalloid; it is a brittle, shiny, black-gray solid that appears to be metallic
but is not. Structurally, silicon resembles dismount (a pure form of carbon).
Silicon is extremely hard, is capable of scratching glass, melts at 1414°C, and boils at 2327°C.
Swedish chemist Jons Jacob Berzelius discovered silicon in 1823. Silicon is the second-most abun-
dant element in the Earth’s crust (oxygen is the most abundant).
Silicon is an element, and silicone is a complex compound. Quartz, sand, agate, jasper, and opal
are silicon oxides. In many compounds, silicon is combined chemically with both oxygen and met-
als. Common examples include talc, mica, asbestos, beryl, and feldspar. Silicon compounds are com-
mercially important, especially the group of compounds known as silicates. Clay, cement, and glass
are silicates. When Si is combined with C, the resulting compound is silicon carbide, a very hard
compound that has many industrial uses. Very pure Si is used in the production of transistors and in-
tegrated circuits.
2.3.2 GROUP VA (15)

2.3.2.1 Arsenic (As)
Arsenic is silvery white, very brittle, and semimetallic. It is toxic to humans, especially the trivalent
compounds. In low doses, arsenic is used as a medication to enhance growth. At low intake levels,
arsenic can accumulate in the body over time. Arsenic is used in bronzing, pyrotechnics, dye manu-
facturing, insecticides, and pharmaceuticals.
An arsenic compound, gallium arsenide (GaAs), has fascinating and useful properties. Because
GaAs can convert electricity directly into laser beams of coherent light, it is used in light-emitting
diodes. These diodes are used in audio disc players and visual display devices. Like silicon, gallium
arsenide is a semiconductor (see Section 1.2 and Appendix B), but because it is more expensive than
silicon, it is not used the manufacture of computer chips. However, GaAs conducts an electrical cur-
rent more rapidly than silicon at the same or lower power, producing less waste heat. When manu-
facturers seek to make chips for computers running at speeds in excess of 100 million instructions
per second, GaAs will be needed.
Groundwater may contain arsenic in high concentrations originating from geological materi-
als. Sources of arsenic pollution are industrial wastes, arsenic-containing pesticides, and smelt-
ing operations.
2.3.2.2 Antimony (Sb)

Antimony is a brittle, crystalline, solid semimetal. It is a poor electricity conductor. The symbol, Sb,
derives from the Latin word stibium. Chemically and biologically, antimony resembles arsenic. It is
used in alloys, and certain compounds are being used for fireproofing textiles, in ceramics and glass-
ware, and as an antiparasitic drug. Antimony and arsenic toxicity symptoms are similar.
2.4 HEAVY METALS

Although the term “heavy metal” has become entrenched in the literature of environmental pollution,
use of the term in this and other contexts has caused a great deal of confusion. One of the most com-
mon definitions of “heavy metal” is a metal with a density greater than 5 g/cm3 (i.e., specific gravity
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> 5). Although relatively clear and unambiguous, this definition causes confusion because it is based
on a rather arbitrarily chosen physical parameter and consequently includes elements with very dif-
ferent chemical parameters. According to other definitions focused on chemical parameters, these el-
ements are classified as class A, class B, and borderline elements.
2.5 METALLIC SUBSTANCES ESSENTIAL TO LIFE

Minerals, including some metals, constitute about 4% of total body weight and are concentrated most
heavily in the skeleton. Minerals known to perform functions essential to life include potassium,
sodium, magnesium, calcium, manganese, cobalt, copper, selenium, zinc, chromium, chloride, io-
dine, and phosphorus.
Other minerals, such as aluminum, silicon, arsenic, and nickel are present in the body, but their
exact functions have not yet been determined. Calcium and phosphorus form part of the structure of
bone, but because minerals do not form long-chain compounds they are otherwise poor building ma-
terials. Their chief role is to help regulate body processes. Calcium, iron, magnesium, and manganese
are constituents of some coenzymes. Magnesium also serves as a catalyst for the conversion of ADP
(adenosine diphosphate) to ATP (adenosine triphosphate). Without these minerals, metabolism halts
and the body dies. Generally, the body uses mineral ions rather than nonionized forms. Some miner-
als, such as chlorine, are toxic or even fatal in the nonionized form.
2.5.1 MOST IMPORTANT METALS IN HUMAN METABOLISM

2.5.1.1 Calcium (Ca)
Calcium is the most abundant cation in the body. It is important to the formation of bones and teeth,
blood clotting, normal muscle and nerve activity, and glycogen metabolism and synthesis, and it
helps prevent hypertension. Vitamin D and lactose help improve calcium absorption by the body.
Oxalic acid, found in some leafy green vegetables (notably spinach), somewhat reduces the absorp-
tion of calcium from those foods.
The recommended daily amount (RDA) for adults is 1200 mg, dropping to 800 mg after age 25.
Sources are dairy products, leafy green vegetables, egg yolks, shellfish, broccoli, canned sardines and
salmon, some types of tofu, and some fortified cereals. In megadoses (ten or more times the RDA),
calcium depresses nerve function and causes drowsiness, extreme lethargy, calcium deposits, and
kidney stones. Hypercalcemia (elevated blood calcium concentrations) occurs in diseases such as hy-
perparathyroidism, sarcoidosis, malignancy, and vitamin D poisoning. Sudden death may occur if
calcium levels remain above 160 mg/l. Calcium toxicity signs and symptoms include anorexia, nau-
sea, vomiting, dehydration, lethargy, coma, and death. Kidney damage and kidney stones may de-
velop in hypercalcemia, and the condition may be associated with congenital heart disease. Excessive
calcium levels in drinking water may be related to the formation of kidney or bladder stones, but there
is no toxicity concern in these cases.
Calcium deficits may cause muscle tetany, osteomalacia, osteoporosis, retarded growth, and
rickets in children. According to a recent survey of studies on various drinking water parameters,
high sodium and low calcium intake have been implicated as factors in the development of high
blood pressure.
2.5.1.2 Iron (Fe)

Iron accounts for 66% of hemoglobin. The hemoglobin in red blood cells carries oxygen (O2) to cells
throughout the body. Hemoglobin is a very large molecule and has four iron (Fe) atoms. Each of these
four atoms is embedded in a part of hemoglobin called heme. The iron atom is in the center. The
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structural formula of heme is illustrated in Figure 2.5. Every hemoglobin molecule has four heme
units, each containing one Fe atom. When hemoglobin picks up O2 in the lungs, each O2 molecule
bonds to one of the Fe atoms.
The bonding ability of Fe in hemoglobin is not restricted to O2. Many other substances can bond
with Fe in hemoglobin, such as the poison carbon monoxide (CO). CO is poisonous because the bond
it forms with Fe is stronger than the O2 bond. When a person breathes in CO, the hemoglobin com-
bines with this molecule rather than with O2. The cells, deprived of O2, can no longer function, and
the person dies.
Only 2 to 10% of dietary iron is absorbed, because of the mucosal barrier. Heme iron, the type
found in meat and other animal products, is better absorbed by the body than nonheme iron, the type
found in foods derived from plants. Consuming a food high in vitamin C enhances the absorption of
iron. The body loses iron in menstrual flow, shed hair, sloughed skin, and mucosal cells. The recom-
mended daily amount (RDA) for males is 10 mg; for females, 18 mg. Normal plasma levels are 1290
µg/l in men and 1100 µg/l in women. The best sources of iron are meat, liver, shellfish, egg yolks,
dried fruits, nuts, legumes, and molasses. Iron is found in virtually every food, with higher concen-
trations in animal tissues than in plants. Generally, men consume about 16 mg/d, and women, about
12 mg/d. Inhalation of urban air contributes about 27 µg/d to total intake.
Megadoses of iron cause hemochromatosis (inherited condition of iron excess), damage to the
liver (cirrhosis and liver cancer), cardiac disorders, and diabetes. Large amounts of stored iron are
associated with an increased risk of cancer because iron serves as a nutrient for cancer cells. Signs of
toxicity are caused by free iron that appears after the carrier is saturated. The first sign of acute tox-
icity is vomiting, followed by gastrointestinal bleeding, lethargy, restlessness, and perhaps gray
cyanosis. If the patient survives for 3 or 4 days, complete recovery follows rapidly.
Chronic excessive iron intake can lead to hemosiderosis (a generalized increased iron content) or
hemochromatosis (specific histological site of hemosiderosis), possibly accompanied by fibrosis.
This condition is relatively benign but may be accompanied by glucose metabolism or exacerbation
of existing cardiac disease. Chronic inhalation of iron fumes leads to mottling of the lungs, a sidero-
sis that is considered benign, nonfibrotic, and not favorable to tubercle bacilli.
CH2 α−Chain β−Chain
H3C CH
C C
HC C C CH
H3C N CH3
C C C C
C N Fe N
C
C C C CH2
OOC CH2 N H
HC C C CH
CH2
C C
H2C CH3
CH2
OOC
FIGURE 2.5 Hemoglobin structure. Hemoglobin consists of four globular protein subunits. Each subunit con-
tains a single molecule of heme, a porphyrin ring surrounding a single ion of iron.
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Inadequate iron intake causes iron-deficiency anemia, pallor, lethargy, flatulence, anorexia,
paresthesia, impaired cognitive performance in children, inability to maintain body temperature, and
reduced production of phagocytic white blood cells (and thus reduced immune system response).
2.5.1.3 Copper (Cu)

Copper is required along with iron for synthesis of hemoglobin. It is also a component of the enzyme
necessary for melanin pigment formation. Humans ingest copper in food and water. Concentrations
in food vary widely from less than 10 to more than 25,000 µg/100 calories, and the maximum con-
taminant level (MCL) in drinking water is 1.0 mg/l.
The RDA is 2 to 3 mg, and the average blood level is 1 mg/l. Rich sources are oysters, liver, kid-
ney, nuts, dried legumes, and potatoes. The average copper content of drinking water is 0.61 to 250
µg/l, and this amount has increased over time due to pipe corrosion and chlorination. Undesirable
taste and odor are often perceived at levels higher than 1 mg Cu/l. Copper is actively absorbed in the
stomach and duodenum.
Acute exposure overdose causes an immediate metallic taste, followed by epigastric burning,
nausea, vomiting, and diarrhea. Symptoms include ulcers and other damage to the gastrointestinal
tract, jaundice, and suppression of urine production. Fatal cases often include secondary effects, such
as hypertension, shock, and coma. Some cases of copper overdose have been the result of consum-
ing large amounts of acidic foods (e.g., fruit juices and carbonated beverages) in copper-lined con-
tainers or dispensed through machines with copper components..
Inhaled dust and fumes cause irritation of the respiratory tract. Chronic exposure may produce
metal fume fever, an influenza-like syndrome that lasts a day or so.
The role of copper in human metabolism involves the turnover of copper-containing enzymes.
Two inherited diseases disrupt these enzymes. Menke’s disease, apparently an inability to absorb
copper, produces copper deficiency. Wilson’s disease is the opposite, leading to excessive accumula-
tion of copper.
2.5.1.4 Sodium (Na)

Of all sodium in the body, 50% is found in extracellular fluid, 40% in bone salts, and 10% in cells.
Sodium is also part of the bicarbonate buffer system and strongly affects distribution of water through
osmosis, thus the acid–base balance of blood. Sodium is necessary in neuromuscular function, as it
is essential for transport of glucose and other nutrients. Absorption is rapid and almost complete. The
hormone aldosterone regulates the metabolism of sodium. Excretion occurs mainly through urina-
tion.
The RDA for sodium has not been established, although daily intake of about 2500 mg is typi-
cal. Sources include table salt (1 tablespoon = 2000 mg), cured meats, and cheese. Excess sodium in-
take causes hypertension and edema. Sodium deficiency is rare but can occur as the result of, for ex-
ample, excessive vomiting, diarrhea, and sweating. Symptoms of sodium deficiency include nausea,
abdominal and muscle cramping, and convulsions.
2.5.1.5 Potassium (K)

Potassium, a principal cation in intracellular fluids, plays a role in the transmission of nerve impulses
and in muscle contraction. Potassium is necessary for proper cardiovascular function, as it helps reg-
ulate blood pressure and water balance in cells. There is some evidence that a high potassium diet
may reduce the risk of hypertension and stroke. The body maintains a high concentration of K+ ions
inside the cells even though K+ concentration outside the cells is low. The reverse is true for Na+. To
prevent K+ from diffusing out of cells and to prevent Na+ from entering the cells, special transport
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proteins in the cell membranes constantly pump K+ into the cells and Na+ out. This pumping requires
energy that is supplied by the hydrolysis of ATP (adenosine triphosphate).
The RDA for potassium has not been established. A diet adequate in calories provides an ample
amount of about 2500 mg/d. Sources are most foods, especially avocados, bananas, dried apricots,
oranges, potato skins, yogurt, meat, poultry, fish, and milk.
Excess potassium usually causes renal failure, severe dehydration, muscular weakness, and car-
diac abnormalities. Deficits are rare but may result from severe diarrhea or vomiting, causing muscu-
lar weakness, paralysis, nausea, tachycardia, or heart failure. In a condition called hypoglycemia, the
body’s output of insulin is elevated and blood sugar is depleted. The condition may suddenly shift the
already small amount of K+ from the extracellular media into the cells. The general result is inadequate
nerve impulses going to the muscles and the extremities. Muscular weakness and numbness in fingers
and toes are symptoms of K+ deficit. Because the heartbeat is also influenced, later symptoms may in-
clude tachycardia (fast heartbeat) and, still later, weak pulse and falling blood pressure. Intravenous
potassium chloride (KCl) solution is used to prevent a severe K+ deficit from causing cardiac arrest.
Sweating causes loss of K+ ions. Hence, strenuous physical activity in warm weather often leads
to severe muscle cramping.
2.5.1.6 Magnesium (Mg)

Magnesium is an important constituent of many coenzymes, is vital to many basic metabolic func-
tions, and also aids in bone growth and the function of nerves, bones, and muscles, including heart
rhythm regulation. In coastal areas, seawater can penetrate drinking-water wells if the water table be-
comes depleted. The water in such wells contains higher-than-normal concentrations of magnesium
salts. These salts, especially magnesium sulfate and magnesium citrate, are incompletely absorbed in
the intestines. High concentration of these salts in the intestines creates a hypertonic condition rela-
tive to neighboring tissues. Consequently, water flows from the tissues to the intestine, diluting the
stool and causing diarrhea. At the same time the tissues are dehydrated. This is also the principle used
in treating hemorrhoids in a sitz bath. When hemorrhoidal tissue is swollen, a hypertonic solution of
magnesium sulfate draws out water and shrinks the tissue. Swollen feet respond to a hypertonic so-
lution when soaked in a hot magnesium sulfate bath.
The RDA for magnesium is 300 to 350 mg. Sources are dairy products, meat, whole-grain cereals,
nuts, legumes, leafy green vegetables, bananas, and apricots. Excess magnesium intake causes diarrhea.
Deficits cause neuromuscular problems, tremors, muscle weakness, irregular heartbeat, diabetes, hy-
pertension, high cholesterol levels, pregnancy problems, and vascular spasms. Low magnesium intake
has been linked to high blood pressure, heart-rhythm abnormalities, and consequently, heart attacks.
2.5.1.7 Zinc (Zn)

Zinc is an important part of many enzymes that are necessary for normal tissue growth and healing
of wounds and the sense of taste and appetite. As a part of peptidase, zinc is important in protein di-
gestion. Zinc is also necessary for prostate gland function. Next to iron, zinc is the second most abun-
dant trace mineral in the body.
The RDA is 15 mg. Sources are seafood, meat, cereal grains, legumes, nuts, wheat germ, whole-
grain bread, and yeast. Zinc excess may raise cholesterol levels and cause difficulty in walking,
slurred speech, hand tremors, involuntary laughter, and a masklike facial expression. Zinc is rela-
tively nontoxic except in extremely high doses. Acidic beverages made in galvanized containers may
produce toxic levels of zinc concentration and can cause nausea, vomiting, stomach cramps, and di-
arrhea. Zinc deficiency may be involved in impaired immunity and learning disabilities and can cause
growth retardation and loss of taste and smell. In general, zinc deficiency is rare, but several groups
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are at risk, such as heavy drinkers (alcohol speeds zinc excretion), athletes (sweating causes signifi-
cant zinc depletion), and strict vegetarians (fruits and vegetables contain little zinc).
2.5.1.8 Manganese (Mn)

Manganese activates several enzymes necessary for hemoglobin synthesis, growth, reproduction,
lactation, bone formation, production and release of insulin, and preventing cell damage. The RDA
is 2.5 to 5.0 mg. The best sources are nuts, legumes, whole grains, leafy vegetables, and fruits.
Excessive manganese appears to contribute to obsessive behavior and hallucinations and may inter-
fere with iron absorption. The effects of manganese deficit are not known.
2.5.1.9 Cobalt (Co)

Cobalt is a constituent of vitamin B12 (see illustration in Figure 2.4) and is needed for erythropoiesis,
the process in which erythrocytes (red blood cells) are formed. Cobalt is found in all cells, with higher
concentrations in bone marrow.
The RDA has not been established. Good sources are liver, lean red meats, poultry, fish, and milk.
Megadoses may cause goiter and damage to the heart muscle. Deficits (mainly impaired absorption)
cause the same symptoms as vitamin B12 deficiency, such as pernicious anemia, weight loss, and neu-
rological disorders.
2.5.1.10 Chromium (Cr)

Chromium is necessary for the proper utilization of sugars and other carbohydrates by optimizing the
production and effects of insulin. It is widely distributed in the body.
The RDA is 0.05 to 2 mg. Sources include liver, meat, cheese, whole grains, yeast, and wine. The
effects of excess chromium are not known. Deficits cause impaired insulin function, hence increased
insulin secretion and the risk of adult-onset diabetes mellitus.
2.5.1.11 Selenium (Se)

Selenium is a nonmetal, listed in the VIA (16) periodic group. An antioxidant, it prevents chromo-
some breakage, certain birth defects, and certain types (e.g., esophageal) of cancer. It is necessary
for the beneficial action of vitamin E; if vitamin E in the diet is inadequate, more selenium is re-
quired. Besides its cancer-prevention activity, selenium slows down the process of aging and makes
heart muscles stronger.
The RDA is 0.05 to 2 mg. Estimated selenium intake is 132 µg/d for an adult man, but in se-
leniferous areas intake may increase to 0.7 to 7 mg daily. The recommended drinking water standard
is 10 µg/l, but the maximum contaminant level goal (MCLG) is 5 µg/l. Selenium dietary supplements
are recommended due to its anticarcinogenic effects. Selenium deficiency occurs when the diet con-
tains less than 0.02 to 0.05 ppm Se. Sources are meat, seafood, and cereals. Selenium content of veg-
etables depends on the concentration of selenium in the soil.
Chronic toxicity has been reported in humans ingesting 1 mg Se/kg/d. Toxic effects include gas-
trointestinal complaints, jaundice, skin hyperpigmentation, hair loss, dental caries, arthritis, dizzi-
ness, and fatigue.
Selenium concentrations in air are high near metallurgical industries. Signs of inhalation expo-
sure are similar to allergenic responses, such as inflammation of mucous membranes and eyes, sneez-
ing, coughing, and frontal headache. Absorption through the skin has not been observed in people
who use antidandruff shampoo containing selenium sulfide.
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Problems resulting from selenium deficits are not well known. People living in the Keshan
province of China suffer from an endemic cardiomyopathy known as Keshan sickness, probably due
to the very low selenium content of the soil.
2.5.2 COMMON PLANT NUTRIENTS

Of the 18 elemental essential plant nutrients, 15 are minerals. Of the 15 minerals, 11 are metals, in-
cluding potassium, calcium, magnesium, boron, copper, iron, manganese, molybdenum, sodium,
vanadium, and zinc. Potassium (K) is needed for enzymatic control of the interchange of sugars,
starches, and cellulose. Calcium (Ca) and magnesium (Mg) are available as Ca2+ and Mg2+ ions.
Chlorophyll requires magnesium; therefore, deficiencies cause chlorosis, or low chlorophyll content.
Iron (Fe) is also an essential catalyst in chlorophyll formation. Green plants suffering from iron de-
ficiency turn yellow. Boron (B) is a trace element and is toxic to most plants in concentrations above
a relatively narrow range. See Appendix D for more information on the roles of metals as plant nu-
trients.
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Toxicity of Metals
3
3.1 GENERAL DISCUSSION OF TOXICITY
Toxic substances, or toxins, are chemicals that adversely affect living organisms. Toxicology is the
study of these effects. Chemical substances exert a wide range of effects, depending on the amount
ingested, inhaled, or absorbed.
3.1.1 TOXICYTOSIS
Toxicytosis is the type and intensity of response evoked by a chemical. To determine the response to
chemicals, the toxicologist administers controlled doses to laboratory test animals and uses the in-
formation to approximate the hazards for humans.
3.1.2 TOXIC EFFECTS

The toxic effects of chemicals are various. Some chemicals interfere with the function of an organ
(e.g., kidneys, lung, or liver), and others disrupt the blood-formation mechanism, enzyme activities,
the central nervous system, or the immune system. For example, dioxin, an extremely toxic com-
pound, affects DNA and ultimately the immune system.
3.1.3 ACUTE EFFECTS

Acute effects are symptoms that appear right after exposure. These effects are generally caused by
fairly high concentrations of chemicals during a short exposure period.
3.1.4 CHRONIC EFFECTS

Chronic effects are delayed, but long-lasting, responses to toxic agents. They may occur months to
years after exposure and usually persist for years. They are generally the result of low-level exposure
over a long period.
3.1.5 LETHAL EFFECTS

Lethal effects can be defined as responses that occur when physical or chemical agents interfere with
cellular and subcellular processes in the organism to such an extent that death directly follows.
Examples are suffocation and interference with movement to obtain food or escape predators.
3.1.6 SUBLETHAL EFFECTS

Sublethal effects disrupt physiological or behavioral activities but do not cause immediate mortality,
although death may follow. Examples include interference with feeding, growth retardation, alter-
ation in blood chemistry, changes in the number and type of blood cells, and tumor formation.
39
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3.1.7 TWO D’S (DOSE AND DURATION)

Toxic effects are determined by the concentration (or dose) of the toxin and the duration of the ex-
posure, known as the two D’s. In general, the higher the dose and the longer the exposure, the greater
the effect.
3.1.8 LD50 (LETHAL DOSE 50)

The dose that kills half of the test animals is called the LD50, or the lethal dose for 50% of the test an-
imals, and is expressed as milligrams of toxin per kilogram of body weight. The lower the LD50, the
more toxic the chemical. For example, a chemical with an LD50 of 200 mg per kilogram of body
weight is half as toxic as one with an LD50 of 100 mg.
3.1.9 CLASSIFICATION OF TOXIC SUBSTANCES

Toxic substances can be classified according to the way in which they disrupt body chemistry.
Modes of toxic substances are described as corrosive, metabolic, neurotoxic, mutagenic, terato-
genic, and carcinogenic.
3.1.9.1 Corrosive Poisons

Corrosive poisons are toxic substances that actually destroy tissues. Examples are strong acids and
alkalis and many oxidants, such as those found in laundry products. Examples are sulfuric acid
(found in auto batteries), hydrochloric acid (also called muriatic acid, used for cleaning purposes),
and sodium hydroxide (used in clearing clogged drains). Some poisons act by undergoing chemical
reaction in the body and producing corrosive material. Phosgene, the deadly gas used during World
War I, is an example. When inhaled, it is hydrolyzed (broken down by water) in the lungs to hy-
drochloric acid, which causes pulmonary edema (a collection of fluid in the lungs) owing to the de-
hydrating effect of the strong acid on tissues, so that oxygen cannot be absorbed effectively by the
flooded and damaged tissues. Some corrosive poisons destroy tissue by oxidizing it. This type of ma-
terial includes ozone and nitrogen dioxide. Selected corrosive poisons and their effects are presented
in Table 3.1.
3.1.9.2 Metabolic Poisons

The word “metabolism” derives from the Greek metabolein, meaning to change or alter. Metabolic
poisons interfere with a vital biochemical mechanism by preventing the proper function of a bio-
chemical mechanism or by completely stopping its activity. For example, carbon monoxide (CO) re-
acts with hemoglobin, making hemoglobin unable to transport oxygen. The cyanide ion (CN–) is the
toxic agent in cyanide salts. One of the most rapidly working poisons, the cyanide ion interferes with
oxidative enzymes, such as cytochrome oxidase. The mechanism of cyanide poisoning is described
in detail in Appendix E.
3.1.9.3 Metal Toxicity

Metal toxicity is the most common of all the metabolic poisons. Metal toxicity is discussed separately
in Section 3.2.
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Toxicity of Metals 41
TABLE 3.1
Selected Corrosive Poisons
Substance Formula Toxic Action Possible Contact Source
Hydrochloric acid HCl Acid hydrolysis Cleaning products
Sulfuric acid H2SO4 Acid hydrolysis dehydrates Auto batteries
tissue, oxidizes tissue
Phosgene ClCOCl Acid hydrolysis Combustion of chlorine-containing
plastics (PVCs)
Sodium hydroxide NaOH Base hydrolysis Caustic soda, drain cleaners
Trisodium phosphate Na3PO4 Base hydrolysis Detergents, household cleaners
Sodium perborate NaBO3.4H2O Base hydrolysis oxidizing agent Laundry detergents, denture cleaners
Ozone O3 Oxidizing agent Ambient air, electric motors
Nitrogen dioxide NO2 Oxidizing agent Polluted air, automobile exhaust
Iodine I2 Oxidizing agent Antiseptics
Hypochlorite OCl— Oxidizing agent Bleach
Peroxide O2–2 Oxidizing agent Bleach, antiseptics
Oxalic acid H2C2O4 Reducing agent Bleach, tanning solutions,
spinach, tea
Sulfite SO2–
3 Reducing agent Bleach
Chloramine NH2Cl Oxidizing agent Produced when ammonia and chlorin-
ated bleach are mixed
Nitrosyl NOCl Oxidizing agent Produced when ammonia and bleach are
mixed
3.1.9.4 Neurotoxins
Neurotoxins are metabolic poisons but their actions are limited to the nervous system. Such poisons
include strychnine, curare (used on darts to bring down game by a group of South American Indians),
atropine, acetylcholine, nicotine, caffeine, codeine, and morphine. Many neurotoxins are useful in
medicine. Atropine is used to dilate the pupil of the eye to facilitate examination of its interior and as
an antidote for anticholinesterase poisons. Atropine sulfate and other atropine salts are excellent
painkillers when applied to the skin. Curare is useful as a muscle relaxant. Nicotine causes stimula-
tion and then depression of the central nervous system. Morphine is the most effective pain reliever
known. Codeine in small quantities is an ingredient in cough syrups.
Chemical warfare agents constitute another group of neurotoxins. The Greeks used sulfur dioxide
gas during the war between Athens and Sparta. Chemical weapons were used in World War I, including
mustard gas (dichloroethyl sulfide), phosgene (Cl2CO), chlorine gas (Cl2), hydrogen cyanide (HCN), and
tabun and sarin nerve gases. In the 1980s, during the war between Iran and Iraq, chemical agents were
also used. Some insecticides, such as parathion and malathion, also qualify as neurotoxins.
3.1.9.5 Teratogens
Teratogens are chemical agents with toxic effects on reproduction; they are classified as radiation,
viral agents, and chemical substances. The study of birth defects caused by chemical agents is called
teratology (terat is a Greek word for “monster”). The thalidomide disaster is a good example of a ter-
atogen. Thalidomide was used as a tranquilizer and sleeping pill. Many pregnant women who took
the drug gave birth to babies with deformities, such as missing arms and fingers. In 1961,
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TABLE 3.2
Teratogenic Substances and Effects on Fetuses of Selected Species
Substance Species Effects on Fetus
Metals
Arsenic Mice, hamsters Increase in males born with eye defects,
renal damage
Cadmium Mice, rats Miscarriage
Cobalt Chickens Eye and lower extremity defects
Gallium Hamsters Spinal defects
Lead Humans, chickens Low birth weight, brain damage, stillbirth,
early- and late-pregnancy death
Lithium Primates Heart defects
Mercury Humans Minamata disease (Japan)
Mice Fetal death, cleft palate
Rats Brain damage
Thallium Chickens Growth retardation, miscarriage
Zinc Hamsters Miscarriage
Organic compounds
DES (diethyl-stilbestrol) Humans Uterine anomalies
Caffeine (15 cups/d equivalent) Rats Skeletal defects, growth retardation
PCBs (polychlorinated biphenyls) Chickens Central nervous system and eye defects
Humans Growth retardation, stillbirth
thalidomide was taken off the market and has not been sold since. Chemicals with teratogenic effects
are listed in Table 3.2.
3.1.9.6 Mutagens
Mutagens are chemical substances that alter the structures of deoxyribonucleic acid (DNA), which
contains the organism’s genes and chromosomes, and cause abnormalities in offspring. In other
words, a mutagen is a chemical that can change the hereditary pattern of a cell and mutation is an
error in the copying of the base sequence of DNA resulting in a change in heredity.
Every embryo formed by sexual reproduction inherits genes from the parent sperm and egg cells.
The transmission of the hereditary information from one generation to the next takes place in the
chromosomes of cell nuclei. Each species has a different number of chromosomes in cell nuclei.
Genes, located inside the chromosomes, contain the information that determines external character-
istics (red hair, blue eyes, etc.) and internal characteristics (blood group, hereditary diseases, etc.).
The genes that carry inheritable traits lie in sequence along the chromosomes.
Chemical analysis shows that nuclei are largely made up of special basic proteins called histones
and a compound called nucleic acids. Only the nucleic acid, DNA, carries hereditary information.
Genes, then, are located in DNA. (See Appendix F for components of nucleic acids.)
In the early 1980s, Bruce Ames and colleagues at the University of California, Berkeley, devel-
oped a simple test (Ames test) that identifies chemicals capable of causing mutations in sensitive
strains of bacteria. In this test, the analyst uses a bacterial strain, such as Salmonella, which feeds on
the amino acid histidine. When the bacteria are grown in a medium that does not contain histidine,
very few survive. If a mutagen is added to the medium, however, some of the bacteria may undergo
mutations that can live without a supply of histidine. The mutated bacteria multiply and show up as
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FIGURE 3.1 Ames test for detecting chemical mutagen.
a heavy growth of bacteria colonies. With such a simple test, many chemicals can be tested for mu-
tagenic activity. Mutagenic chemicals can then be further tested in animals to determine whether they
are also carcinogens. The Ames test is illustrated in Figure 3.1.
3.1.9.7 Carcinogens
Carcinogens are chemicals that cause cancer, an abnormal growth condition in an organism. The rate
of cell growth in cancerous tissue differs from the rate in normal tissue. Cancerous cells spread to
other tissues and show partial or complete loss of specialized functions. Almost all human cancers
caused by chemicals have a long induction period, which makes it extremely difficult for researchers
to obtain meaningful interpretation of exposure data.
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FIGURE 3.2 Carcinogenic aromatic hydrocarbons.
About 200 years ago, London surgeon Percivall Pott found that chimney sweeps (boys employed
to clean chimneys) were especially prone to cancer of the scrotum and other parts of the body. Today,
it is known that these cancers were caused by fused aromatic hydrocarbons present in the chimney
soot. Carcinogenic aromatic hydrocarbons have at least four rings and at least one angular junction
(see Figure 3.2). These carcinogens are produced by automobile exhausts and are found in cigarette
smoke. Researchers have verified the carcinogenic behavior of a large number of chemicals, some of
which are listed in Table 3.3. In addition to industrial chemicals that are known to contaminate air
and drinking water, our everyday diets contain a great variety of natural carcinogens. Some of these
chemicals are also mutagens and teratogens. For example, celery contains isoimpinellin — a mem-
ber of the chemical family called psoralens — at a level of 100 µg/100 g. This level increases 100-
fold if the celery is diseased. Psoralens, when activated by sunlight, damage DNA. Oil of bergamot,
which is found in citrus fruits, contains a psoralen that was once used by a French manufacturer of
suntan oil. Sunlight caused the psoralens to enhance tanning. Black pepper contains small amounts
of safflere, a known carcinogen. Oil of mustard and horseradish contain allyl isothiocyanate, which
is mutagenic and carcinogenic.
3.2 METAL TOXICITY

Heavy metals are perhaps the most common of all metabolic poisons. The mechanism of metal tox-
icity is different from other metabolic poisons. Metal toxicity can affect enzymes, the cellular pro-
teins that regulate many important chemical reactions. Heavy metals are toxic primarily because they
react with and inhibit sulfhydryl (SH) enzyme systems, such as those involved in the production of
cellular energy. Figure 3.3 illustrates the reaction of a heavy metal with glutathione. The metal re-
places the hydrogen in two sulfhydryl groups on adjacent molecules and the strong bond effectively
eliminates the two glutathione molecules from further reaction.
TABLE 3.3
Selected Inorganic Chemicals Carcinogenic to Humans
Compound Use or Source Site Affected
Arsenic and compounds Insecticides, alloys Skin, lungs, liver
Asbestos Brake linings, insulation Respiratory tract
Beryllium Alloy with copper Bone, lungs
Cadmium Metal plating Kidneys, lungs
Chromium Metal plating Lungs
Nickel Metal plating Lungs, sinuses
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FIGURE 3.3 Glutathione reaction with a metal. (From World of Chemistry, 1st ed., by M.D. Joesten, D.O.
Johnston, J.T. Netterville, J.L. Wood © 1990. Reprinted with permission of Brooks/Cole, an imprint of the
Wadsworth Group, a division of Thomson Learning. Fax 800 730-2215.)
A disturbance in enzymatic activity can seriously alter the functioning of the organ or tissue. As
examples, mercury and arsenic both bind to certain enzymes, thereby blocking their activity. Lead
binds to the thiol (SH–) chemical group in the enzymes and consequently reduces the body’s ability
to synthesize enzymes necessary for respiration. The addition of chelating agents is used to eliminate
such metal poisoning. Transition metals are known for their ability to form many complex ions —
substances in which a metal cation is surrounded by and bounded to one or more other ions or
molecules. Complexes are often called chelates (from the Greek chele, meaning “claw”) because a
chelating agent encases an atom or ion like a crab grasps food. In the same way a chelating agent en-
velops a metal ion, and when the metal ion is tied up, the sulfhydryl groups are freed and the enzyme
again functions normally. For example, an effective chelating agent for removing lead from the
human body is ethylenediamine-tetraacetic acid (EDTA). The calcium disodium salt of EDTA is
used in the treatment of lead poisoning because EDTA by itself would remove too much of the blood
serum’s calcium. In solution, EDTA has a greater tendency to complex with lead (Pb2+) than with cal-
cium (Ca2+). As a result, the calcium is released and the lead is tied up in the complex, as seen in
Figure 3.4. The lead chelate is then excreted in the urine.
FIGURE 3.4 Structure of chelate formed when the anion of the

EDTA envelopes a Pb2+ ion. (From World of Chemistry, 1st ed.,
by M.D. Joesten, D.O. Johnston, J.T. Netterville, J.L. Wood ©
1990. Reprinted with permission of Brooks/Cole, an imprint of
the Wadsworth Group, a division of Thomson Learning. Fax
800 730-2215.)
L1572_C03 5/23/02 1:19 PM Page 46
Metals can form lipid-soluble organo-metallic ions, involving Hg, As, Sn, Tl, and Pb, capable of
penetrating biological membranes and accumulating within cells. Some metals in metallo-proteins
exhibit oxidation-reduction activity, such as Cu2+ to Cu+, which can alter structural or functional in-
tegrity. Certain metals displace others in biomolecules. For example, when Zn2+ is replaced by Ni2+
or Be2+ to Mg2+ in enzymes, the enzymes are deactivated. In addition, the replacement of Ca2+ with
other metals in membrane proteins causes functional disorders.
Because heavy metals are elements, they cannot be broken down, either chemically or by de-
composer organisms. The only ways to dispose of them are to dilute them to levels at which they are
no longer toxic or to treat them with chemicals that convert them into less toxic compounds.
3.3 TOXIC EFFECTS OF SELECTED REPRESENTATIVE METALS

3.3.1 GROUP IA (1): ALKALI METALS
3.3.1.1 Lithium (Li)
Lithium is widely found in plant and animal tissues. Daily intake has been estimated at 2 mg/d.
Therapeutic doses of lithium (used as an antidepressant) range from 90 to 1800 mg/d. When patients
are first dosed with lithium carbonate, they often experience nausea, vomiting, and abdominal pain
about an hour after each dose, but these symptoms soon disappear.
Chronic toxicity usually affects the gastrointestinal tract, nervous system, and kidneys.
Additional symptoms of acute toxicity include increased thirst, excessive salivation, and diarrhea.
Chronic toxicity effects include tremors (especially of the hands), muscular weakness, ataxia, giddi-
ness, drowsiness, muscular hyperirritability and fasciculation, lethargy, stupor, and, in extreme cases,
coma and seizures. Renal symptoms include polyuria, elevation of nonprotein nitrogen, and, in the
terminal stages, oliguria. An increase in a rare cardiac defect, Ebstein’s anomaly, has been reported
in children of women dosed therapeutically with lithium.
3.3.1.2 Sodium (Na) and Potassium (K)

See Section 2.5.
3.3.1.3 Rubidium (Rb)

Rubidium is present in the body in larger than trace metal amounts and can replace potassium in cer-
tain processes, but the body’s requirement of this metal is not known. It functions similarly to potas-
sium in altering heart muscle contractions and can alter behavior and manic-depressive states, but its
metabolic function is not understood. All animal tissues contain 20 to 40 ppm (mg/kg) of this metal.
The toxicity of rubidium appears to be relatively low.
3.3.1.4 Cesium (Cs)

Cesium is able to substitute for potassium to some extent. For example, cesium partially protects the
kidneys and heart in potassium-deficiency conditions, and it concentrates in erythrocytes, as does
potassium. Almost half the average daily intake of about 10 mg/d derives from food (red meats, eggs,
and dairy products). Its toxicity is not known.
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3.3.2 GROUP IIA (2): ALKALINE EARTH METALS

3.3.2.1 Beryllium (Be)
Beryllium inhibits a number of enzymes. A small intake of beryllium from water and soil (via food)
occurs, estimated at 100 µg/d. Airborne beryllium is the result of coal combustion, cigarette smoke,
and, in a few areas, beryllium-processing plants. The toxic effects of beryllium are ascribed to dam-
age of lysosomes, which release cell-destroying enzymes. Chronic exposure to beryllium and its
compounds can produce a frequently fatal pulmonary granulomatosis called berylliosis. Major signs
and symptoms include pneumonitis with accompanying cough, chest pain, and general weakness and
often pulmonary dysfunction. The first symptom is shortness of breath.
3.3.2.2 Magnesium (Mg) and Calcium (Ca)

See Section 2.5.
3.3.2.3 Strontium (Sr)

Strontium substitutes for calcium in many normal mechanisms, often with no apparent ill effects.
Strontium is concentrated in the skeleton. Dietary strontium intake ranges from 0.98 to 2.2 mg/d for
adults, about one third of which is from milk. Acute strontium toxicity causes death from respiratory
failure, but most strontium compounds have a low toxicity. Evidence of chronic effects is negligible.
3.3.2.4 Barium (Ba)

Barium is absorbed through the lungs and the gastrointestinal tract and, once absorbed, accumulates
in the bones. Small proportions of barium accompany calcium in virtually every foodstuff. It is esti-
mated that the average daily intake is 1.33 mg. The national interim primary drinking water standard
is 1 mg/l. Barium is commonly found in urban ambient air, because barium compounds are used as
diesel fuel, smoke suppressants, and automotive lubricants.
The soluble salt of barium causes toxicity. Soluble salts are irritants to skin and mucous mem-
branes, and the barium dispersant in automotive lubricants is a mild eye irritant. Barium compounds
(nitrate, sulfide, carbonate, and chloride) have been involved in accidental and suicidal poisonings.
Signs are nausea, vomiting, colic, and diarrhea, followed by myocardial and general muscular stim-
ulation with tingling of the extremities. Severe cases continue to loss of tendon reflexes, heart fibril-
lation, general muscular paralysis, and death from respiratory arrest. A fatal dose of barium chloride
(BaCl2) for a human is 0.8 to 0.9 g (0.55–0.6 g Ba).
Chronic exposure to barium causes a benign pneumoconiosis, known as baritosis (numerous
evenly distributed nodules in the lungs), which has occurred in workers exposed to finely ground bar-
ium sulfate (BaSO4). Baritosis nodules usually disappear after cessation of exposure, but bronchial
irritation may persist. Barium is mutually antagonistic to all muscular depressants.
3.3.3 GROUP IIIA (13): BORON–ALUMINUM (B–AL)

3.3.3.1 Aluminum (Al)
Aluminum is found in all human tissues, but is most concentrated in the lungs, presumably from in-
haled air. Oral doses of aluminum induce phosphorus depletion syndrome and deplete red blood cell
ATP (adenosine triphosphate). Unprocessed foods contain aluminum in very small quantities, al-
though some vegetables and fruits may contain up to 150 mg/kg. Total daily intake is estimated at
about 80 mg.
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Aluminum compounds are used for storing and processing food (e.g., baking powder, cooking
vessels, and metal foil). Inhalation of aluminum compounds has been used in the prevention of sili-
cosis. Aluminum compounds are also used to prevent hyperphosphatemia in renal disease. High alu-
minum intake originates from packaging, aluminum cooking vessels, aluminum foil, and aluminum-
containing antacids.
Aluminum is generally considered nontoxic. Because Alzheimer’s disease patients have a high
aluminum content in certain brain cells, research is now focused on high aluminum intake as a pos-
sible causal factor. In patients with this disease, the nerve fibers in the cerebral cortex are entangled,
and some of the nerve endings degenerate and form plaque. The brain becomes smaller, and part of
the cortex atrophies.
3.3.3.2 Gallium (Ga)

Gallium is chiefly deposited in bone tissue and is relatively immobile. Human exposure to gallium
has included the use of radioactive plus stable gallium in therapeutic doses, so reported toxicity may
be due to radioactivity. Signs of toxicity include dermatitis, gastrointestinal disturbances, and bone
marrow loss.
3.3.3.3 Indium (In)

The daily human intake from food is estimated at less than 8 µg. Indium is the lowest-volume
metal used by the body. Drinking water is unlikely to be the major source of human exposure.
However, indium might be expected to leach from galvanized iron pipes. No drinking water con-
centrations have been reported. Fish and shellfish containing bioconcentrated indium from con-
taminated waters can lead to human oral exposure. Lead-smelting emissions can produce elevated
indium levels in ambient air. Soluble and colloidal indium compounds are generally more toxic
than insoluble noncolloidals.
3.3.3.4 Thallium (Tl)

Thallium at low concentration as Tl+ has an affinity for certain enzymes and an activating ability ten
times that of K+. Thallium salts inhibit several enzymes that play major roles in bone formation. Toxic
doses adversely affect protein synthesis and cause disaggregation of ribosomes. Consumption is
about 0.5 ton/year and is not well defined. Biota in thallium-contaminated areas currently have thal-
lium levels (>3 ppm) that could be high enough to cause toxic symptoms in mammals if their entire
diet derives from the contaminated biota. Accidental poisonings have occurred from use of thallium
rodenticides, but their use has been banned. The use of thallium acetate as a cosmetic depilatory
around 1930, as well as its use for about 50 years as a therapeutic epilant in the treatment of fungal
scalp infections, was often accompanied by severe poisoning and fatalities.
Dermal exposure to thallium may occur while handling thallium preparations used in laboratory
analyses. After acute poisoning, the kidneys — especially the renal medulla — contain the highest
thallium concentrations. In the final stages of fatal poisoning, thallium appears in all organs and tis-
sue concentrations tend to equalize. For humans, doses of 14 mg/kg and above are fatal. In mammals,
toxic effects are usually delayed for 12 to 48 h.
Symptoms include gastrointestinal discomfort, pain and paralysis in the extremities, high blood
pressure, optic nerve dystrophy and blindness, psychic excitement (10 days after poisoning), liver
and kidney damage, and hair loss. In the absence of known association of the patient with possible
sources, diagnosis of thallium poisoning is difficult. The usual cause of death is respiratory arrest, the
end result of pneumonia and general respiratory depression. Other deaths from thallium poisoning
have been attributed to cardiac failure, dehydration, and progressive impairment of the brain and
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vagus nerve. In still other cases, severe parenchymatous changes were found, including fatty heart
and liver (degenerative changes due to fat deposits in cells), lung edema, meningeal congestion, renal
damage, gastroenteritis, and widespread degeneration of the nerve cells and axons in the brain.
Few of the reported human and mammalian studies of thallium toxicity provide conclusions
about the dangers of very low chronic intake (10 to 20 µg/d). In humans, alopecia is the hallmark of
long-term thallium poisoning, with hair loss beginning within about 10 days and epilation being
complete within a month. However, alopecia does not always occur, even after severe poisoning.
Selenium- and sulfur-containing compounds may offer some protection against thallium toxic-
ity. The only proven antidote to date is Prussian blue (potassium ferrihexacyano-ferrate(II)).
3.3.4 GROUP IVA (14): CARBON

3.3.4.1 Tin (Sn)
Daily intake of tin from food ranges from 0.2 to 10 mg. SnF2 in toothpaste is another oral source. Tin
in food may be augmented by tin leached from unlacquered cans. The general population inhales up
to 7 µg/d from ambient air. Toxic effects have been seen in people who eat canned food, with accu-
mulations of 250 mg Sn per kg or more. Tin toxicity may cause nausea, vomiting, and diarrhea.
Organotins are more toxic than inorganic compounds. Contact with tin compounds may cause skin
irritation. The only lethal incident associated with tin compounds mentioned in the literature at the
time of this writing was the Stalinon catastrophe in France, in which about 100 people died from in-
gesting an impure, untested drug preparation that was contaminated with triethyltin.
3.3.4.2 Lead (Pb)

Lead is toxic to the nervous system, and children are especially susceptible to its effects. Lead is read-
ily absorbed through the intestinal tract and deposited in the central nervous system. The first lead
water pipes were used in ancient Rome by upper-class citizens; their children drank the water
throughout childhood and thus were at high risk of lead toxicity. This fact may explain the bizarre
behavior of certain notorious emperors and may have contributed to the fall of the Roman Empire.
In recent years, exposure to lead toxicity has become widespread. Sources are lead-containing paint,
air, soil, dust, food, and drinking water. The presence of lead in the body is indicated by lead blood
levels, expressed as micrograms of lead per deciliter of blood (µg/dl). Blood lead levels of 10 µg/dl
and higher may contribute to decreased cognition, nervous system damage, and stunted growth.
Many children have suffered lead poisoning after ingestion of lead-based paint. Lead-based paint was
used inside many homes until Congress passed the Lead-Poisoning Prevention Act in 1971.
Lead concentrations as high as 0.4 to 0.8 mg/l in natural waters — mostly from natural sources,
such as galena deposits — have been reported. High contamination levels may be caused by indus-
trial and mining pollution sources. High levels of lead in drinking water consist mainly of corrosion
products from lead service pipes, solders, and household plumbing. Lead as a corrosion product in
drinking water is associated with copper. Copper is needed for good health, and at low levels it has a
beneficial effect, but in high concentration it is toxic, causing diarrhea and vomiting. The maximum
contaminant level (MCL) established for lead in drinking water is 0.02 mg/l, but the maximum con-
taminant level goal (MCLG) for lead is zero, and for copper is 1.3 mg/l.
Acute toxicity is quite unusual, as lead is a relatively insoluble, cumulative poison. Reported
symptoms include fatigue, sleep disturbance, and constipation, followed by colic, anemia, and neu-
ritis. Symptoms of chronic lead poisoning include loss of appetite, metallic taste, constipation, ane-
mia, pallor, malaise, weakness, insomnia, headache, irritability, muscle and joint pains, tremors, en-
cephalopathy, and colic. Some lead-poisoning victims develop weakness in the extensor muscles,
known as wrist drop or foot drop.
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Lead interacts with a number of other metals. A typical detoxification treatment involves chela-
tion of the lead with calcium ethylenediamine tetraacetate (EDTA) given parenterally. Repeated
treatments leach lead out of bone tissue. Lead arthralgia (joint pains) is lead-induced gout caused by
lead’s interference with uric acid excretion by the kidneys. Lead toxicity affects the kidneys and
causes tubular dysfunction, or nephrotoxicity. Lead is associated with the depression of many en-
docrine functions, particularly the thyroid and adrenal glands. It causes premature deliveries and
spontaneous abortions in humans, as well as chromosome aberrations, but there is no evidence of ter-
atogenic or carcinogenic effects.
3.3.5 GROUP VA (15): NITROGEN–PHOSPHORUS (N–P)

3.3.5.1 Bismuth (Bi)
Bismuth is not available in food. Drinking water contains an average of 0.01 mg/l. Certain over-the-
counter drugs sold for gastrointestinal disturbances contain bismuth compounds (e.g., Pepto-
Bismol). Bismuth, as BiOCl, is used as a white pearlescent coloring material in lipsticks and
other cosmetics.
3.4 TOXICITY OF SELECTED TRANSITION METALS

3.4.1 PERIOD 4
3.4.1.1 Scandium (Sc)
Scandium intake from food and drinking water is considered negligible. Recently, intake by inhala-
tion found in Italy was 0.04 µg/d. No toxic effects have been found.
3.4.1.2 Titanium (Ti)

Titanium levels in food vary widely; total daily intake has been estimated at between 300 to 600 µg
and 100 to 1600 µg. The highest titanium concentrations are found in butter and corn oil. Typically,
intake from drinking water is about 2 µg/d, and from inhalation about 2 to 4 µg/d from ambient air.
Titanium dioxide is only slightly absorbed. Titanium dioxide and metal are practically inert.
3.4.1.3 Vanadium (V)

Vanadium concentrations in animal and plant foods are very low, probably a few parts per billion
(ppb) in wet weight, and are also very low in drinking water. Vanadium in the ambient air results from
combustion of coal, crude oils, and undersulfurized heavy-fuel oils; airborne vanadium doubles dur-
ing cold weather. The highest vanadium concentrations in the body have been found in the lungs.
Vanadium salts have intermediate inhalation toxicity and low oral toxicity. Industrial exposures are
generally described as acute episodes with relapses and sometimes chronic coughing and bronchitis.
Sequelae of acute vanadium intoxication may include chronic respiratory symptoms, but pneumoco-
niosis, fibrosis, and emphysema do not develop.
Epidemiological investigations have correlated concentrations of vanadium and other metals in
ambient air with disease mortality indexes. V, Cd, Zn, Sn, and Ni in the air of 25 localities correlated
well with heart disease and nephritis. V, As, and Zn in the air showed a weak association with lung
cancer. V was strongly associated with bronchitis, V and Be with pneumonia; V, Be, and Mo corre-
lated with other cancers.
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Exposure to vanadium irritates the skin and eyes, and a greenish-black discoloration of the
tongue and oral mucosa may occur with a salty or metallic taste. These symptoms disappear 2 to 3
days after cessation of exposure.
3.4.1.4 Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co),

Copper (Cu), and Zinc (Zn)
These elements are discussed in Chapter 2.
3.4.1.5 Nickel (Ni)

Nickel uptake is mostly from food at 300 to 500 µg/d. Airborne nickel derives from combustion of
coal and petroleum products. High concentrations are found in the brain, liver, and kidneys. The
major toxicity responses to lead and lead compounds are contact dermatitis and allergic sensitization,
but generally nickel and nickel compounds have little toxicity. Nickel itch usually begins with a sen-
sation of burning and itching, followed by erythema and a nodular eruption, which may progress to
pustules or ulcers. Once exposure ends, recovery occurs in about a week. This reaction is found
mostly in women who use nickel-plated garter clips (before the panty hose era) and costume jewelry,
especially earrings.
Inhalation of nickel carbonyl causes pulmonary disturbances and sometimes death. Chronic ex-
posure to nickel dust, nickel compounds, or a combination of compounds causes cancer of the respi-
ratory tract and lungs. Nickel in drinking water also correlates with mortality from oral and intestinal
cancer, but not from respiratory cancer.
3.4.2 PERIOD 5
3.4.2.1 Yttrium (Y)
Yttrium is discussed in Section 3.4.3 together with the lanthanides (rare earth metals).
3.4.2.2 Zirconium (Zr)

Zirconium uptake is mostly from meat, poultry, eggs, dairy products, algae, and shellfish. However,
plants generally do not translocate zirconium above the roots, so only root crops would be affected.
Zirconium in lipstick, nonaerosol deodorants, and poison ivy remedies also contribute to oral intake.
Zirconium contamination of superphosphate fertilizers is a possible route into human foodstuffs.
Information on zirconium in the ambient air is scarce, but it is likely present because of its high nat-
ural background concentration in the soil. Little or no hazard is expected from its emission.
Niobium (Nb), also known as in metallurgical industry as columbium, has been found in the diet
at levels of 600 µg/d and in drinking water, at about 20 µg/d. Niobium is found in almost every food
— meat, cereals, dairy products, fish, vegetables, and fruits — but concentrations are above average
in tea, coffee, pepper, and fats. Occupational exposure occurs is ore processing, metal fabrication,
and welding. No toxic effects in human have been reported as of this writing.
3.4.2.2 Molybdenum (Mo)

Daily intake of Mo is about 100 to 500 µg. The main dietary contributors are meat, grains, and
legumes. Concentrations in drinking water average about 1.4 µg/l (based on the drinking water of
100 large cities). Toxicity is negligible for molybdenum, with the exception of the hexavalent com-
pounds ( molybdenum valence ranges from 0 to +6). A gout-like disease has been observed in
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people living in a region of Armenia characterized by high ambient levels of Mo; dietary intake in
this region is 10 to 15 mg/d.
3.4.2.3 Ruthenium (Ru)

No information is available on the toxicity of oral, dermal, or inhalation exposure to Ru.
Ruthenium red is a tumor inhibitor, apparently because it interferes with mitochondrial transport
of calcium.
3.4.2.4 Rhodium (Rh)

There is no information available about the toxicity of oral, dermal, or inhalation exposure to Rh. The
effectiveness of rhodium chloride (RhCl3) as an antiviral chemotherapy has been variously explained
by the ability to act as a cobalt antagonist and to form lipid-soluble complexes, which interfere with
phospholipid formation by the virus (Browning 1969).
3.4.2.5 Palladium (Pd)

Palladium used in dental alloys is innocuous. Dental uses include pins in porcelain teeth, dental
wires, and gold alloys for inlays, crowns, bridges, and partial dentures. Information on dermal or in-
halation exposure is not available. The (ineffective) use of colloidal palladium to treat tuberculosis
and gout has no adverse effects.
3.4.2.6 Silver (Ag)

Oral exposure mainly occurs through drinking water. Natural waters do not contain toxic levels of
silver (over 0.05 mg/l). Silver at 0.1 to 0.2 mg/l was used in the Apollo space program and on Soviet
spacecraft to purify drinking water and wastewater. Numerous silver-containing medications and
dental silver amalgam fillings have contributed to high levels of oral exposure; however, at present
these uses are banned. A few drops of silver nitrate are applied to the conjunctiva of newborn infants
to prevent ophthalmia neonatorum, a result of gonorrhea transmitted from the mother. Silver salt so-
lutions and ointments are used to treat burns.
Absorption does not occur through contact with the skin. Inhalation from ambient air near mines
and smelters and from occupational exposure causes problems. The major problem in humans from
overexposure to silver is argyria, characterized by a blue-gray coloration of the skin, mucous mem-
branes, and internal organs. The disease has occurred almost exclusively among workers in the man-
ufacture of silver nitrate (AgNO3). Argyrosis of the conjunctiva has occasionally developed from the
use of silver-nitrate-containing hair dyes for coloring the eyebrows and eyelashes.
3.4.2.7 Cadmium (Cd)

Daily consumption of cadmium varies from 17 to 64 µg according to various national estimates.
Concentrations in drinking water range from 0.2 to 0.7 µg/l. Airborne cadmium comes primarily
from the steel industry and waste incineration, followed by volcanic activity and zinc production.
There is no evidence of dermal absorption, and oral absorption is very low. The effects of acute ex-
posure to cadmium include vomiting (15–30 min after ingestion), increased salivation, abdominal
pain, and diarrhea. Acute inhalation toxicity is characterized by coughing and tightness in the chest
(4–10 h after exposure). Chronic exposure produces a variety of effects on kidneys, lungs, heart,
bones, and gonads. Cadmium fumes can damage the olfactory organs. Cadmium toxicity is decreased
by the presence of other metals, especially zinc, calcium, copper, iron, and selenium.
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3.4.3 PERIOD 6
3.4.3.1 Lanthanum (La) and Lanthanides or Rare Earth Elements: Cerium (Ce),
Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm),
Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho),
Erbium (Er), Thullum™, Ytterbium (Yb), and Lutetium (Lu)
Yttrium (Y) and the lanthanides are discussed as group because of their chemical and toxicological
similarities. The naturally occurring rare elements range from 0.2 to 46.1 ppm for cerium (Ce). No
information is available on oral and dermal exposure; inhalation is possible from ambient air. All lan-
thanides deposit in the bones and liver. No definitive evidence of poisoning has been reported.
Lanthanum as La3+ counteracts Ca2+ binding in heart muscle.
The blood anticoagulant activity of the lanthanides has been studied for the prevention of throm-
bosis. The anticoagulant effect of the lanthanide salts is counteracted by vitamin K.
3.4.3.2 Hafnium (Hf)

Information on exposure to hafnium is the same as for zirconium (see Section 2.2).
3.4.3.3 Tantalum (Ta)

Tantalum is relatively nontoxic.
3.4.3.4 Tungsten (W)

Tungsten is basically inert. No information is available for oral, dermal, or inhalation exposure.
There is no evidence of acute toxicity. Chronic exposure to WC (tungsten carbide) in grinding
wheels produces hard metal disease, with symptoms of coughing, dyspnea, wheezing, minor radi-
ological abnormalities, and asthma. The disease is primarily attributed to the cobalt content of WC
(see Section 2.2).
3.4.3.5 Rhenium (Re)

No information is available for oral, dermal, or inhalation exposure.
3.4.3.6 Osmium (Os)

Inhalation exposure is expected near burning or smelting of copper concentrates. Acute effects of os-
mium tetroxide (OsO4) in humans include a purulent discharge and eye and respiratory damage; per-
manent and temporary blindness can develop. Toxic exposure occurs among precious metal workers
and histologists who use OsO4 solution as tissue stain. Some workers have reported contact dermati-
tis, and some arthritis patients treated with OsO4 have also developed dermatitis. Injections of OsO4
solution into knee joints of patients afflicted with rheumatoid arthritis affect chemical synovectomy
— the solution destroys the synovial membrane and allows regeneration of a thickened synovial
membrane. OsO4 articular injections are toxic; thus, great care must be taken in handling OsO4 be-
fore injection to avoid inhalation by medical personnel or the patient.
3.4.3.7 Iridium (Ir)

Iridium is chemically similar to rhodium (Rh). No information is available on exposure or toxicity.
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3.4.3.8 Platinum (Pt)

Oral exposure is unknown. After inhalation, lung clearance is rather slow, and kidney and bone tis-
sues accumulate platinum. Some people develop allergic dermatitis upon wearing platinum jewelry.
Platinosis, which resembles an allergic hypersensitivity that improves upon removal from exposure,
is an asthma-like condition with dermatitis. A low-grade fibrosis in the lungs may also develop in
platinosis. Irritation of the eyes and upper respiratory tract is common, with coughing, tightness of
the chest, wheezing, and shortness of breath. In the most severe cases, cyanosis, diaphoresis, feeble
pulse, and clammy coldness of the extremities are possible.
3.4.3.9 Gold (Au)

Oral exposure commonly originates from dental inlays and crowns. It is doubtful that these mate-
rials contribute any gold to the “body burden” (general metabolism), as attrition and leaching are
unlikely. No information is available on inhalation exposure. Dermal irritation and eczema may de-
velop from contact with gold jewelry. Colloidal gold compounds are used to treat arthritis. Contact
with or injections of gold compounds may cause chronic contact-sensitivity dermatoses.
3.4.3.10 Mercury (Hg)

Major exposure via oral ingestion occurs through eating fish. Mercury levels are usually below 200
mg/g in fish and below 20 mg/g in other foods. Total intake of inorganic mercury is estimated at less
than 10 µg/d. Dermal exposure is minimal, although mercury compounds used for disinfecting dia-
pers may cause mercury poisoning. The main organs infected are the brain and kidneys.
Mercury is poisonous and, to make matters worse, mercury and its salts accumulate in the body.
Because mercury is a cumulative poison, even small amounts absorbed over extended periods can
lead to serious medical problems. Acute mercury poisoning is usually the result of toxic exposure to
soluble inorganic salts. After gastrointestinal disturbances (abdominal pain, nausea and vomiting,
bloody diarrhea, and shock), stomatitis, and loosening of the teeth, nephritis and hepatitis occur.
Death results from ulceration and bleeding in the gastrointestinal tract. Mercury vapors cause erosive
bronchitis and bronchiolitis with interstitial pneumonia. Mercurialism, or chronic intoxication by el-
emental mercury vapor or mercury salts, is much more common than acute toxicity, due to the cu-
mulative nature of mercury. Symptoms include mental and emotional disturbances (the victim be-
comes depressed and excitable and irascible, especially when criticized), headache, fatigue, weak-
ness, loss of memory, drowsiness, insomnia, muscular tremor, and general neuralgia. Other symp-
toms are gingivitis, stomatitis, digestive disturbances, and ocular lesions. Symptoms of toxicity from
exposure to mercury salts are similar, but kidney disorders are more frequent. Metallic mercury —
the type found in thermometers, sphygmomanometers, and other instruments — is not absorbed by
the gastrointestinal tract and therefore is not very hazardous if swallowed. However, it is absorbed by
lung tissue. Therefore, mercury vapors are hazardous, especially when heated.
Mercury poisoning has become an acute problem in recent years because of industrial dumping
of mercury compounds into streams and lakes. Previously it was believed that mercury, as a heavy
metal, would settle to the bottom of lakes and rivers and would be harmlessly buried there, covered
by sand. However, certain microorganisms convert mercury metal to organic mercury compounds,
mainly methylmercury and dimethylmercury. Dimethylmercury evaporates quickly from the water,
but methylmercury remains in the bottom sediments and is slowly released into the water, where it
enters organisms in the food chain and is biologically magnified (by buildup of chemical elements or
substances in organisms in successively higher trophic levels). Methylmercury is concentrated in
fish, and people who eat the contaminated fish can get mercury poisoning.
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When mercury was dumped in the Minamata Bay, Japan, ethylmercury and other alkylmercury
compounds produced Minamata disease, which has the clinical appearance of encephalitis. The earli-
est signs are gradual decreases in the senses of touch, vision, hearing, and taste; numbness in the fin-
gers, toes, lips, and tongue; and tunnel vision (which develops to complete blindness). Other signs are
loss of balance, lack of coordination, and tremor and mood changes, similar to mercurialism. Of the 52
reported cases in Japan, 17 people died and 23 were permanently disabled. Once contaminated foods
were removed from the market, the number of mercury-poisoning cases reported dropped drastically.
Metallic mercury is mixed vigorously with silver to form amalgams used in tooth fillings.
Significant mercury exposure may result upon opening amalgamators (amalgam-mixing devices).
Mercury is also released when dentists carve and shape amalgams. Overall, dentists and dental
assistants experience prolonged exposure, compared to patients’ intermittent exposure. In the nine-
teenth century, the felt industry used mercury(II) nitrate (Hg(NO3)2), to stiffen the felt used in mak-
ing hats. The factory workers frequently developed tremors or hatter’s shakes and lost hair and teeth;
hence, the term “mad hatters.” A vivid description of the psychological changes produced by mer-
cury poisoning can be found in Lewis Carroll’s Alice in Wonderland, specifically the Mad Hatter
character.
Mercury is a byproduct of manufacturing vinyl chloride and is also emitted in the aqueous wastes
of chemical manufacture, incinerators, power plants, laboratories, and even hospitals. Organic mer-
cury compounds continue to be used as fungicides in seeds for planting crops. In one severe outbreak
in New Mexico, a family consumed a pig that had eaten contaminated seeds. Mercury intoxication is
treated by chelation (see Section 3.2).
3.4.4 SELECTED METALS OF PERIOD 7, INCLUDING ACTINIDES

3.4.4.1 Thorium (Th)
Major oral exposure occurs in medical use of thorium as a radiopaque medium, and some patients
have developed tumors. Drinking water contains no thorium. Dermal and inhalation exposures are
found mostly in workers handling thorium compounds. The effect of chronic exposure to thorium
is radiotoxicity.
3.4.4.2 Uranium (U)

All naturally occurring uranium isotopes are radioactive. Daily intakes in urban areas of various coun-
tries have been estimated at 1.0 to 1.5 µg/d. Major food sources of uranium are table salt, vegetables,
and cereals. Drinking water is also important source of uranium intake in areas with overlying uranium
deposits. Oral toxicity is low, but inhalation is highly toxic. UF4 is the most toxic by inhalation and
U2O8 the least toxic. Long-term exposure results in a high radiation hazard. Absorbed uranium deposits
in bone tissue, where it is bound in the hydroxyapatite complex, substituting for calcium.
3.5 TOXICITY OF SELECTED METALLOIDS
3.5.1 BORON (B)

Oral intake originates mostly from boric acid and sodium borate used as food preservatives. Boron
is an important plant nutrient (especially for tobacco, cabbage, and sugar beets); therefore, most food
is rich in boron. Seawater has a relatively high boron concentration, as do algae and sea sponges.
Boron participates in the hormonal regulation of calcium and plays an important role in cell division.
Boric acid, whether from ingestion or skin absorption, causes nausea, vomiting, diarrhea, abdominal
cramps, and erythematous lesions on skin and mucous membranes. High doses cause circulatory
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TABLE 3.4
Selected Arsenic-Containing Insecticides
Insecticide Formula
Lead arsenate Pb3(AsO4)2
Monosodium methanarsenate CH3–AsHO–O–O–.Na+
Paris green (copper acetoarsenite) 3 CuO.3 As2O3.Cu(C2H3O2)2
collapse, tachycardia, cyanosis, delirium, convulsions, and coma. Chronic exposure may cause dry
skin, eruptions, and gastric disturbances.
3.5.2 GERMANIUM (GE)

The daily intake of germanium from food is about 1.5 mg. Because of its presence in coal ash,
urban air may contain germanium. This metalloid is nontoxic; toxic effects result only after intake
of high doses.
3.5.3 ARSENIC (AS)

Trace quantities are usually found in food and water, and the highest concentrations occur in seafood.
Arsenic is a feed additive for swine and poultry. Dietary intake ranges from 0.15 to 0.40 mg/d.
Arsenic is released into the air by coal combustion and the use of arsenic-containing pesticides.
Table 3.4 presents selected arsenic-containing insecticides.
During metabolism arsenic is methylated to methylarsinic acid (cacodylic acid) and mono-
methylarsenic acid, thereby detoxifying arsenic. Acute effects are caused by accidental, suicidal,
or homicidal ingestion of large doses. The effects of arsenic overdose are collapse caused by high
blood pressure, restlessness, convulsions, coma, and death. Effects of chronic exposure, either en-
vironmental or occupational, are carcinogenesis, cardiovascular disease, and neurological distur-
bances. Effects on the mucous membrane, peripheral nervous system, and gastrointestinal system
are quite common.
Selenium is capable of reducing the carcinogenicity of arsenic, perhaps even eliminating it.
Arsenic’s effect on various enzymes is based on the reaction between the metal and the thiol chemi-
cal group in the enzymes and cofactors (such as glutathione). A compound known as British Anti-
Lewisite (BAL) was developed as an antidote to Lewisite, an arsenic-containing poison gas used in
World War I. BAL is a chelating agent that bonds to the metal at several sites. The chelation of ar-
senic by BAL is illustrated in Figure 3.5. With the arsenic or heavy metal tied up, the sulfhydryl
FIGURE 3.5 BAL chelation of As or heavy metal ion. (From World of Chemistry, 1st ed., by M.D. Joesten,
D.O. Johnston, J.T. Netterville, J.L. Wood © 1990. Reprinted with permission of Brooks/Cole, an imprint of the
Wadsworth Group, a division of Thomson Learning. Fax 800 730-2215.)
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groups in vital enzymes are freed and can resume their normal functions. BAL is used routinely to
treat heavy metal poisoning.
3.5.4 ANTIMONY (SB)

Antimony belongs to the same periodic group as arsenic and resembles it chemically and biologi-
cally. Oral exposure to antimony occurs primarily through foods. Daily intake ranges from 10 to
1250 µg/d. Drinking water also contains antimony in trace quantities; the maximum acceptable
limit is 146 µg/l. Concentrations of antimony in the air of large U.S. cities averages 32 ng/m3.
Tobacco contains 0.1 mg/kg antimony by dry weight, so cigarette smoke also contributes to inhala-
tion exposure. Dermal contact may occur from textiles that have been fireproofed by antimony com-
pounds. Medical uses include radioantimony injections and antimony compounds in the treatment
of parasitic diseases.
According to the literature (1977), children ingesting about 30 mg/l antimony from contaminated
soft drinks suffered vomiting, nausea, and diarrhea. The effect from inhalation exposure is distur-
bance of the upper respiratory tract. Exposure to heavy antimony fumes causes vomiting, abdominal
cramps, and diarrhea. Long-term exposure may participate in the development of gastrointestinal and
lung problems and heart disease.
3.5.5 TELLURIUM (TE)

Tellurium intake occurs mostly from fatty foods, some processed foods, baking powder, and bever-
ages. Tellurium has not been found in drinking water and ambient air. The toxicity of tellurium has
been observed in accidental poisoning and exposure of research animals. Effects included garlic
breath, digestive disturbances, stunted growth, somnolence, and loss of hair.
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Standards Related
4 to Metallic Pollutants
The increasing number of the toxic pollutants in the environment has become a major problem. Over
the years, many laws have been enacted to protect the environment and human health. The
Environmental Protection Agency (EPA) is the federal government regulatory agency charged with
managing and enforcing environmental protection legislation issued by Congress. The EPA sets stan-
dards for permissible levels of pollutants and continuously updates them. Metals are powerful pollu-
tants, and they are perhaps the most common metabolic poisons. Teratogenic and carcinogenic ef-
fects of some metals are also well known. (Metals with teratogenic and carcinogenic effects are listed
in Tables 3.2 and 3.3, respectively). Therefore, metals are important components of regulatory stan-
dards related to diverse different environmental matrices.
4.1 ENVIRONMENTAL LAW

Environmental law is more than simply a collection of statutes on environmental topics. It can best
be described as an interrelated system of statutes, regulations, guidelines, factual conclusions, and
case-specific judicial and administrative interpretations. The environmental law system is an organ-
ized way of using all aspects of the legal system to minimize, prevent, punish, or remedy the conse-
quences of actions that damage or threaten the environment and public health and safety. The envi-
ronmental law system, then, includes the Constitution, statutes, regulations, rules of evidence, rules
of procedure, judicial interpretations, common law, and, indeed, criminal law, to the extent that these
elements are being applied toward environmental ends. In summary, environmental law encompasses
all environmental protections that emanate from the following sources:
• Laws, including federal and state statutes and local ordinances

• Regulations promulgated by federal, state, and local agencies
• Court decisions interpreting laws and regulations
• Common law
• U.S. Constitution and state constitutions
• International treaties
4.1.1 FEDERAL AND STATE ENVIRONMENTAL LAW

Many federal statutes establish regulatory programs under which the states have the opportunity to
enact and enforce laws meeting minimum federal criteria to achieve the regulatory objectives estab-
lished by Congress. States are generally the primary permitting and enforcement authorities and are
subject to federal intervention only if they do not enforce effectively or rigorously enough. The laws
and interpretations used to apply and enforce federal laws vary considerably from state to state and
these variations may not be readily apparent. Many states provide their citizens and environment with
protections beyond minimum federal criteria.
59
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4.1.2 ENVIRONMENTAL REGULATIONS

Environmental statutes generally empower an administrative agency, such as the EPA, to develop and
promulgate regulations. Rule making is a process of adopting regulations. Final regulations are pub-
lished in the Federal Register. The regulations are consolidated annually into the Code of Federal
Regulations (CFR).
4.1.3 SELECTED REGULATORY PROGRAMS

The major federal environmental statutes define most of the substantive compliance obligations of
the environmental law system. Programs created by federal statutes are aimed at protection and ap-
propriate management of environmental systems, such as groundwaters, surface waters, and drink-
ing water quality. Examples of federal statutory programs are summarized below.
4.1.3.1 Clean Water Act (CWA)

The CWA controls the discharge of toxic materials into surface streams. The act regulates pollution
levels by setting discharge limits and water quality standards. The concept of federal discharge per-
mits was incorporated into the National Pollutant Discharge Elimination System (NPDES). The EPA
set up 34 industrial categories covering over 130 toxic pollutants that are discharged into surface wa-
ters. Entities responsible for discharges of these substances are required to use the best available
technology (BAT) to achieve discharge limits. Toxic and hazardous wastes discharged directly to a
receiving body of water are regulated by NPDES permits, whereas materials acceptable to an indus-
trial or municipal sewer system are discharged without a federal permit. The CWA also includes
guidelines to protect wetlands from dredge-and-fill activities.
4.1.3.2 Safe Drinking Water Act (SDWA)

The SDWA was established to protect groundwaters and drinking water sources. The EPA estab-
lished maximum contaminant levels (MCLs) and maximum contaminant level goals (MCLGs) for
each contaminant that may affect human health. The SDWA includes over 83 contaminants, grouped
as inorganic chemicals, synthetic organic chemicals, and microbiological and radiological contami-
nants. It also regulates the injection of liquid wastes into underground wells to ensure that disposal
methods do not damage the quality of groundwater and groundwater aquifers. Details of this program
are discussed later in this chapter.
4.1.3.3 Resource Conservation and Recovery Act (RCRA)

The primary concern of this program is to protect groundwater supplies by creating a management
system for hazardous waste, from the time it is generated until it is treated and disposed of. Waste
that contains chemicals on EPA’s list of toxic chemicals may be deemed hazardous waste.
4.1.3.4 Toxic Substances Control Act (TSCA)

The EPA has the authority to control the manufacture of chemicals. The TSCA bans the manufacture
of polychlorinated biphenyls (PCBs) and also controls the disposal of these chemical substances
(40 CFR, Parts 712–799).
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Standards Related to Metallic Pollutants 61
4.1.3.5 Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)

The FIFRA controls the manufacture and use (i.e., registration process) of pesticides, fungicides, and
rodenticides (40 CFR, Parts 162–180). Examples of canceled-registration chemicals include DDT,
kepone, and ethylene dibromide (EDB).
4.1.3.6 Comprehensive Environmental Response, Compensation, and

Liability Act (CERCLA, Superfund)
This program is designed to address the problems of cleaning up existing hazardous waste sites.
CERCLA provides the EPA with “broad authority for achieving clean-up at hazardous waste sites”
and the clean-ups are financed jointly by private industry and the government (Superfund). According
to CERCLA, substances which “when released into the environment may present substantial danger
to the public health or welfare or the environment” are hazardous. CERCLA establishes a list of sub-
stances that, when released in sufficient amounts, must be reported to the EPA.
The Superfund Amendments and Reauthorization Act (SARA) of 1986 pertains to carcinogen
testing and regulations. Section 121 requires that clean-ups at Superfund sites “[a]ssure protection of
human health and the environment.” SARA provides authority and financing to the EPA to act
quickly in the event of hazardous material spills.
Title III, Section 313 of SARA, the Emergency Planning and Right To Know Act, requires pri-
vate-sector and public-sector facilities to report annually to the EPA on the types of hazardous sub-
stances they handle and all releases of such compounds into various media (e.g., air and water).
Program enforcement is provided by state governments after receiving EPA approval.
4.2 DRINKING WATER STANDARDS

The correct definition of drinking or potable water is water delivered to the consumer that can be
safely used for drinking, cooking, and washing. Regulatory agencies establish physical, chemical,
bacteriological, and radiological quality standards for potable water. Water supplies in the United
States and elsewhere are endangered by the introduction of new chemicals and pollutants every year.
Drinking water standards in the United States, established by the EPA, reflect the best scientific and
technical judgment available.
The World Health Organization (WHO), a U.N. agency dedicated to public health, first issued
Guidelines for Drinking-Water Quality in 1984–1985 as a basis for developing standards that, if
properly implemented, would ensure the safety of drinking water supplies. Although the main pur-
pose of these guidelines is to provide a basis for developing standards, the guidelines are also useful
to countries in implementing alternative control procedures where the implementation of drinking
water standards is not feasible.
4.2.1 SAFE DRINKING WATER ACT (SDWA)

Drinking water quality is protected by laws and regulations that must be enforced. Currently about
200,000 public water systems are regulated under the Safe Drinking Water Act (SWDA). The rest of
the population is served by private wells not subject to regulation under SDWA. Drinking water risks
are the highest priority of public health issues because everyone drinks water and because so many
potentially toxic substances can contaminate drinking water. In accordance with the SDWA, the EPA
sets standards as close as possible to a level “at which no known or anticipated adverse effects on the
health of persons occur and which allows an adequate margin of safety.” Systems that fail to meet
MCLs must be treated using the BAT. Under the revised SDWA, it will be easier for the EPA to en-
sure that the states take enforcement actions swiftly and effectively.
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The federal SDWA requires a broader appreciation of the “philosophy” of water. Water utility serv-
ice is distinguished from all other types of utilities in three important ways: (1) water service is the only
utility essential for life; (2) unlike other utilities, water is ingested; and (3) the investment in facilities
per customer to provide water service far exceeds the comparable cost for other utility services.
The content of water in terms of aesthetics (taste, color, and odor) and health-risk contaminants
is the result of natural processes, external pollutants, or byproducts of accepted water treatment
methodologies. For example, iron, manganese, and radium naturally occur in some groundwater.
Pollutants such as nitrates and pesticides can be found in surface waters and arise from stormwater
runoff and drainage. Disinfection byproducts can result from chlorination at a treatment plant pur-
suant to methodology accepted and mandated for a hundred years. The SDWA places the burden on
water utilities to treat water content, regardless of “contamination” source.
On August 5, 1998, the EPA published guidelines on the definition of a public water system
under the SDWA. In the same publication, the EPA stated that bottled and packaged water and natu-
ral bodies of water that have been altered by humans fall under the jurisdiction of the SDWA.
4.2.2 SDWA REGULATIONS

Drinking water regulations fall into primary and secondary categories. Primary regulations are
aimed at protecting public health, and define “clean” water. Secondary regulations are intended to
protect the “public welfare” by offering unenforceable guidelines on the taste, odor, or color of
drinking water, among other considerations. Primary and secondary drinking water standards are
listed in Table 4.1.
4.2.2.1 Maximum Contaminant Levels (MCLs) and Maximum Contaminant

Level Goals (MCLGs)
The MCLs are enforceable standards that must be established as close to respective MCLGs as is fea-
sible. “Feasible” means with the use of the best technology, treatment techniques, and other available
means, while taking cost into consideration. The 1986 amendments to the SDWA require the EPA to
establish national primary drinking water regulations (NPDWRs) for 83 specified contaminants with
MCLs and MCLGs. In addition, the EPA must publish a list of contaminants that may require regu-
lation every 5 years, beginning in February 1998. At 5-year intervals, the EPA must determine
whether to regulate at least five of the listed unregulated contaminants.
4.2.3 SDWA AMENDMENTS

Since 1986, regulatory impact analyses have been developed for amending the SDWA. The changes
are discussed below.
4.2.3.1 Fluoride Studies

In 1986 and 1990, the EPA requested new toxicological studies about the health effects of fluoride to
determine whether the current standard was adequate (Fed. Reg., 51, 11396, April 1986; Fed. Reg.,
55, 160, 3 January 1990). Besides the existing 4-mg/l primary standard, the EPA established a sec-
ondary standard with an MCL of 2 mg/l. According to study results, the previous 4-mg/l MCL for
fluoride is adequate as a primary standard.
4.2.3.2 Volatile Organic Compounds (VOCs) Rule

The VOCs rule that went into effect in 1989 (Fed. Reg., 52, 23690, 8 July 1987; Fed. Reg., 53, 25108,
1 July 1988) established standards for eight compounds. The EPA suggested new regulations,
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including changes in analytical methods and laboratory certification and the redesign of monitoring
programs of unregulated contaminants by using targeted sampling.
4.2.3.3 Surface Water Treatment Rule (SWTR)

Promulgated in 1989, the SWTR is currently in effect. Utilities served by surface water or ground-
water under the direct influence of surface water should monitor disinfectant concentration and dis-
infectant contact time and, based on summaries of collected data, submit a proposal for the
Disinfectant–Disinfectant By-Products Rule (Fed. Reg., 54, 27488, 29 June 1989) to set MCLGs for
Giardia, viruses, and Legionella. SWTR also established treatment techniques for surfacewater sup-
ply sources and ground water under direct influence of surface water, including filtration and disin-
fection requirements. In addition, the rule set turbidity standards. Filtration is required unless crite-
ria are met for avoidance (Fed. Reg., 54, 27486–27541, 29 June 1989).
As required under the 1996 SDWA amendments, the Interim Enhanced Surface Water Treatment
Rule was issued in December 1998. The purpose of the rule is to improve the control of microbial
pathogens in drinking water. It is expected that this rule will further reduce the occurrence of
Cryptosporidium, Giardia, and other waterborne bacteria or viruses in finished drinking water sup-
plies. This rule applies to public water systems that use surface water or ground water under direct
influence of surface water and serve at least 10,000 people. The rule also requires primacy states to
conduct sanitary surveys for all surfacewater and groundwater systems, regardless of size.
In 2000, the EPA issued its Long Term 1 Enhanced Surface Water Treatment and Filter Backwash
Proposed Rule (Fed. Reg., 65, 19046, 10 April 2000). The purpose of the proposed rule is to increase
protection of finished water from contamination by cryptosporidium and other microbial pathogens.
The proposal is intended to extend the rule to small systems serving less than 10,000 people.
4.2.3.4 Groundwater Disinfection Rule

Another proposed rule that has been pending for several years provides for groundwater disinfection.
In May 2000, the EPA published its proposed rule (Fed. Reg., 65, 30193, 10 May 2000). Its objective
is to provide a companion rule for groundwater sources of supply to the surfacewater treatment rule.
Thus, the rule is likely to include MCLGs of zero, disinfection treatment techniques in lieu of MCLs,
and so on. It may also include provisions for natural disinfection. The proposed rule provides a treat-
ment that achieves a minimum 99.99% inactivation rate on virus removal. A final regulation was an-
ticipated in November 2000. Currently, only surfacewater systems and systems using groundwater
under the direct influence of surface water are required to disinfect water supplies.
4.2.3.5 Total Coliform Rule (TCR)

Promulgated in 1989 (Fed. Reg., 54, 27547, 29 June 1989), the TCR is currently in effect. The rule
established approved analytical methods for Escherichia coli bacteria. Under the TCR, microbiolog-
ical samples should be iced during transportation and overviews of sampling points performed. Any
coliform-positive sample should be resampled and the test repeated within 24 h of notification. The
MMO-MUG (Colilert) test should be run on selected selected samples, and another accepted method
should be run to check the effectiveness of the MMO-MUG test.
4.2.3.6 Synthetic Organic Chemicals (SOCs) and Inorganic Chemicals (IOCS)

The rule for synthetic organic chemicals (SOCs) and inorganic chemicals (IOCs) was finalized in
1991. Proposed MCLs for aldicarb, aldicarb sulfoxide, and aldicarb sulfon were scheduled for 1994.
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TABLE 4.1
Drinking Water Standards
MCl Analytical Detection Limit

Parameters (mg/l) Method (mg/l)
Inorganics Primary Standards

Arsenic 0.05 EPA 206.2 0.0020
Barium 2.00 EPA 200.7 0.0140
Cadmium 0.005 EPA 200.7 0.0010
Chromium 0.10 EPA 200.7 0.0090
Cyanide 0.20 EPA 335.2 0.0050
Fluoride 4.00 EPA 340.2 0.01
Lead 0.015 EPA 239.2 0.0010
Mercury 0.002 EPA 245.1 0.0002
Nickel 0.100 EPA 200.7 0.0110
Nitrate nitrogen 10.00 EPA 353.2 0.01
Nitrite nitrogen 1.00 EPA 354.2 0.01
Selenium 0.05 EPA 270.2 0.0010
Sodium 160 EPA 200.7 0.226
Antimony 0.006 EPA 204.2 0.0020
Beryllium 0.004 EPA 200.7 0.0020
Thallium 0.002 EPA 279.2 0.0010
Organics
Trihalomethanes
Bromoform — EPA 502.2 0.00013
Chloroform — EPA 502.2 0.00005
Dibromochloromethane — EPA 502.2 0.00013
Dichlorobromomethane — EPA 502.2 0.00007
Total THMs 0.10 EPA 502.2
Volatiles
1,2,4-Trichlorobenzene 70 EPA 502.2 0.310
cis-1,2-Dichloroethylene 70 EPA 502.2 0.0300
Xylenes (Total) 10,000 EPA 502.2 0.170
Dichloromethane 5 EPA 502.2 1.40
o-Dichlorobenzene 600 EPA 502.2 0.140
p-Dichlorobenzene 75 EPA 502.2 0.190
Vinyl chloride 1 EPA 502.2 0.290
1,1-Dichloroethylene 7 EPA 502.2 0.170
trans-1,2-Dichloroethylene 100 EPA 502.2 0.180
1,2-Dichloroethane 3 EPA 502.2 0.0400
1,1,1-Trichloroethane 200 EPA 502.2 0.0300
Carbon tetrachloride 3 EPA 502.2 0.0400
1,2-Dichloropropene 3 EPA 502.2 0.0400
Trichloroethylene 3 EPA 502.2 0.0400
1,1,2-Trichloroethane 5 EPA 502.2 0.0400
Tetrachloroethylene 3 EPA 502.2 0.0800
Monochlorobenzene 100 EPA 502.2 0.0700
Benzene 1 EPA 502.2 0.0500
Toluene 1000 EPA 502.2 0.0800
Ethylene benzene 700 EPA 502.2 0.0600
Styrene 100 EPA 502.2 0.0700
Pesticides and PCBs 2 EPA 508 0.01
Lindane 0.2 EPA 508 0.01
Methoxychlor 40 EPA 508 0.02
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TABLE 4.1 (Continued)

MCl Analytical Detection Limit
Parameters (mg/l) Method (mg/l)
Toxaphene 3 EPA 508 0.2

Dalapon 200 EPA 515.1 1
Diquat 20 EPA 549 4
Endothal 100 EPA 548 10
Glyphosate 700 EPA 547 10
Di(2-ethylhexyl)adipate 400 EPA 506 1
Oxamyl (Vydate) 200 EPA 531.1 0.5
Simazine 4 EPA 507 0.1
Picloram 500 EPA 515.1 0.2
Dinoseb 7 EPA 515.1 0.2
Hexachlorocyclo-pentadiene 15 EPA 512 0.1
Carbofuran 40 EPA 531.1 0.5
Atrazine 3 EPA 507 0.1
Alachlor 2 EPA 507 0.3
2,3,7,8-TCDD (Dioxin) 0.00003
Heptachlor 0.4 EPA 508 0.01
Heptachlor epoxide 0.2 EPA 508 0.01
2,4-D 70 EPA 515.1 0.5
2,4,5-T (Silvex) 50 EPA 515.1 0.05
Hexachlorobenzene 1 EPA 508 0.01
Di(2-ethylene hexyl)-phthalate 6 EPA 506 1
Benzo(a)pyrene 0.2 EPA 550 0.01
Pentachlorophenol 1 EPA 515.1 0.05
PCB 0.5 EPA 508 0.05
Dibromochloropropane 0.2 EPA 504 0.005
Ethylene dibromide 0.02 EPA 504 0.005
Chlordane 2 EPA 508 0.05
Radiological analysis
Gross alpha 5 pCi/l EPA 900.0 —
Radium-226 15 pCi/l EPA 900.0 —
Radium-228 50 pCi/l EPA 900.0 —
Microbiology
Total coliform Zero count/100 ml
Secondary Standards
Aluminum 0.200 EPA 200.7 0.100
Chloride 250 EPA 300.0 0.5
Copper 1.00 EPA 200.7 0.0040
Iron 0.30 EPA 200.7 0.0500
Manganese 0.05 EPA 200.7 0.0050
Silver 0.10 EPA 200.7 0.0050
Sulfate 250 EPA 300.0 0.0100
Zinc 5.00 EPA 200.7 0.0140
Color 15 C.U. SM 204A 5.00
Odor 3 TON SM 207 1.00
pH 6.5–8.5 EPA 150.1 —
Total dissolved solids (TDSs) 500 EPA 160.1 10.0
Foaming agents 0.5 SM 512B 0.0500
Note: SDWA regulations are not health related. They are intended to protect the “public welfare” by offering unen-
forceable guidelines on the taste, odor, or color of drinking water. Recommended levels are intended mainly to maintain
and provide aesthetic and taste characteristics.
MCl = maximum contaminant level; CU = color unit; TON = threshold odor number; pCi/l = picoCurie per liter; µg/l =
micrograms per liter; 2,4-D = dichlorophenoxyacetic acid; 2,4,5-T = trichlorophenoxyacetic acid; PCD = polychlori-
nated biphenyls.
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In 1993, the MCL and MCLG for atrazine were revised at the request of Ciba-Geigy, the manufac-
turer of this chemical (Fed. Reg., 56, 3600, 30 January 1991; Fed. Reg., 56, 30266, 1 July 1991).
4.2.3.7 Lead and Copper Rule

This rule defines the action level for lead and copper, establishing monitoring requirements for cor-
rosion control, selecting sampling sites, issuing deadlines for public-education information, requir-
ing monitoring data to be reported to the state, and clarifying which certified laboratories must be
used. Monitoring for lead and copper requires the collection of first-draw water samples at taps
within consumers’ premises. However, most lead and copper content in finished water results from
piping, soldering, fixtures, and appliances within consumers’ premises over which water utilities
have no control. The rule shifts the responsibility for these conditions from consumers to the utility.
It imposes on a utility the obligation to proactively control its water through such corrosion control
techniques as adjustment to pH, alkalinity, and calcium and additions of phosphates and silicates.
Under the rule, the MCLG for lead is zero, and the action level is 0.015 mg/l. For copper, both
the MCLG and action level are 1.3 mg/l, with a nonenforceable MCLG of 1.0 mg/l.
The EPA made what it described as “minor changes” to the lead and copper rule in January 2000.
The changes are summarized below:
Clarifications for systems that optimize corrosion control and continue to maintain and oper-
ate any corrosion control already in place
Requirement for utilities subject to replacing the lead service-line portions they own to notify
residents of lead-level potential in drinking water where the service line is only partially re-
placed
Revisions of analytical methods and monitoring and reporting requirements
A single national standard for lead is not suitable for every public water system because the con-
ditions of plumbing materials, which are the major source of lead in drinking water, vary across sys-
tems and the systems generally do not have control over the sources of lead in their water. In these
circumstances, the EPA suggests that requiring public water systems to design and implement cus-
tomized corrosion control plans for lead will result in optimal treatment of drinking water overall,
that is, treatment that deals adequately with lead without causing public water systems to violate
drinking water regulations for other contaminants (Fed. Reg., 56, 26487).
4.2.3.8 Sulfate Standard

Sulfates appear to have no adverse chronic health effects. The only impacts are diarrhea and result-
ing dehydration. The EPA has issued a secondary MCL of 250 mg/l for sulfates. Sulfates are included
on the EPA’s first list of contaminants for possible regulation. Under the current secondary MCL, the
utility should provide public education to protect infants, new residents, and tourists. Bottled water
can solve this problem.
4.2.3.9 Arsenic Proposal

One of the EPA’s most controversial proposals pertains to arsenic: MCLG of zero and MCL of 0.005
mg/l (Fed. Reg., 65, 38887, 22 June 2000). Arsenic can occur naturally as well as in industrial emis-
sions and effluents. The EPA’s proposed minimum levels have been criticized as lacking a scientific
basis and being too rigorous upon consideration of compliance costs.
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4.2.3.10 Radio Nuclides

The EPA was under court order to promulgate a uranium NPDWR by November 2000. A draft guid-
ance manual pertaining to the anticipated rule on radionuclides was released May 3, 2000. The pri-
mary concerns that delayed the issuance of a final rule were the costs and benefits of regulating
radon.
4.2.4 NATIONAL SECONDARY DRINKING WATER REGULATIONS (NSDWRS)

The NSDWRs relate to the aesthetics of water, not health effects. These regulations specify maxi-
mum levels of a component to ensure a color, taste, or odor that will not cause users to discontinue
its use. Secondary maximum contaminant levels (SMCLs) do not cause health risks. At levels above
SMCLs, the contaminants may cause users to perceive water to have adverse aesthetic effects, in-
cluding taste, color, odor, and cosmetic impacts, such as skin or tooth discoloration, staining, and cor-
rosivity. SMCLs are not enforceable as a matter of federal law. However, some states have adopted
SMCLs, or regulations above or below SMCLs, as enforceable standards. For example, complaints
about iron staining (iron content higher than NSDWRs of 0.3 mg/l constitutes a violation) are com-
mon at the state level.
4.3 SURFACEWATER STANDARDS

Freshwater ecosystems fall into two categories — lakes and ponds, and flowing systems, such as
rivers and streams. Lakes and ponds are more susceptible to pollution because the water is replaced
at a slow rate. Complete replacement of a lake’s water may take 10 to 100 years or more, and during
these years pollutants may build up to toxic levels. In rivers and streams, the water flow easily purges
pollutants. If the pollution is continuous and distributed uniformly along river and stream banks, the
cleaning effect by purging does not work well.
Rivers, streams, and lakes contain many organic and inorganic nutrients needed by the plants and
animals that live in them. These nutrients in higher concentrations may become pollutants. Organic
pollutants derive from feedlots, sewage treatment plants, and certain food-processing industries
(dairy products, meat packing, etc.). The increased organic matter stimulates the growth of bacteria,
which in turn consume the organic matter, and thus help clean up pollution. Unfortunately, bacteria
use up oxygen and therefore reduce dissolved oxygen in the water. The lack of dissolved oxygen kills
fish and other aquatic organisms, and the aerobic (oxygen-requiring) bacteria population changes to
anaerobic (nonoxygen-requiring) bacteria. Anaerobic bacteria produce foul-smelling and toxic gases
such as methane and hydrogen sulfide. This process in rivers and streams occurs more readily dur-
ing the hot summer months. When the organic pollutants are used up, and additional pollutants do
not enter the water body, oxygen levels return to normal via oxygen from the air and oxygen released
by plants during photosynthesis.
Organic pollutants nourish bacteria and certain inorganic pollutants stimulate the growth of
aquatic plants. These pollutants are called nutrients, and include nitrogen as ammonia and nitrate,
and phosphorus as phosphates. These compounds derive from fertilizers, laundry detergents, and
sewage treatment plants. High levels of these nutritional compounds can lead to the dense growth of
aquatic plants and thick mats of algae covering lakes and rivers. Excessive plant growth negative af-
fects fishing, swimming, boating, and navigation activities. Aerobic bacteria decompose these plants
when they die. The lowered dissolved oxygen content of the water kills aquatic organisms and leads
to anaerobic bacteria growth, which in turn produces odorous and toxic gases. Thus, inorganic and
organic pollutants cause the same problems in surface waters.
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Classification of surface waters is based on water quality and use. The five main groups of sur-
face waters are listed below:
Class I: Potable water supplies

Class II: Shellfish propagation or harvesting
Class III: Recreation — propagation and maintenance of healthy, well-balanced population of
fish and wildlife
Class IV: Agricultural water supply
Class V: Navigation, utility, and industrial use
Groundwater contamination via flow from surfacewater is well known. surfacewater flows from
open bodies (rivers and lakes) can enter into aquifers where groundwater levels are lower than sur-
facewater levels. The opposite situation — ground water contaminating surface water — is also pos-
sible, and occurs when the water table is high or the surface water is lowered by pumping wells.
Monitoring, maintaining, and regulating the quality of surface waters is the responsibility of state
governments.
4.3.1 CLEAN WATER ACT (CWA)

The CWA is the primary federal statute that addresses water pollution in the United States. The
Refuse Act of 1899 was the first federal law affecting water pollution. The Refuse Act, while not a
major element of the current federal water pollution control program, is still in effect. The roots of
the CWA can be traced to the Federal Water Pollution Control Act of 1972. Amendments to the act
in 1987 created new programs for controlling toxins, established stormwater regulation, strengthened
water-quality-related requirements, and established a loan fund for construction of sewage treatment
plants. In 1990, in response to the Exxon Valdez oil spill, Congress overhauled the oil spill provisions
of the act in the Oil Pollution Act of 1990, sometimes referred to as OPA 90.
4.3.1.1 CWA Objectives, Goals, and Policy

The objective of the CWA is to “restore and maintain the chemical, physical, and biological integrity
of the nation’s waters.” To achieve this objective, the act establishes the following goals:
• Elimination of the discharge of pollutants into surfacewaters

• Achievement of a level of water quality that “provides for the protection and propagation
of fish, shellfish and wildlife” and “for recreation in and on the water”
The act also establishes a national policy, which states that “the discharge of toxic pollutants in toxic
amounts shall be prohibited.”
4.3.1.2 Pollutants as Defined by CWA

As defined in the CWA, pollutants include dredged spoil; solid waste; incinerator residue; sewage;
garbage; sewage sludge; munitions; chemical wastes; biological materials; heat; wrecked or dis-
carded equipment; rock; sand; cellar dirt; and industrial, municipal, and agricultural waste dis-
charged into water. Despite this specific definition, the term has been broadly interpreted by the
courts to include virtually any material, as well as characteristics such as toxicity and acidity.
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4.3.1.3 Point Source as Defined by CWA

According to the CWA, a point source is “any discernable, confined and discrete conveyance ...
from which pollutants are or may be discharged.” This definition has been interpreted to cover al-
most any natural or manufactured conveyance from which a pollutant may be discharged, including
pipes, ditches, erosion channels, and gullies. Vehicles, such as bulldozers or tank trucks, have also
been included among point sources. Human beings are not point sources, at least for purposes of
criminal enforcement of the act. In other words, a person dumping pollutants into a water body,
other than through hose or pipe, for example, would not be in violation of the act’s prohibition of
discharges from point sources without a permit. The person may, however, be in violation of other
laws and regulations.
4.3.1.4 National Pollutant Discharge Elimination System (NPDES) Permit

The NPDES permit program implements the CWA prohibition on unauthorized discharges by re-
quiring a permit for every discharge of pollutants in U.S. waters. Permits, which are issued by the
EPA or authorized state government agencies, give the permittee the right to discharge specified pol-
lutants from specified outfalls, normally for a period of 5 years. Currently, 14 states and territories
have received permitting authority (40 CFR, 123.24). The implementation and enforcement of the
NPDES program depend to a large extent on self-monitoring. Permits require dischargers to monitor
their own compliance with permit limitations on a regular basis and to report the results of this mon-
itoring to the permitting authority.
4.3.1.5 Water Quality Standards

Water quality standards are established by the states. The CWA requires all states to classify the wa-
ters within the state according to intended use (see Section 4.3).
Water quality criteria quantitatively describe the physical, chemical, and biological characteris-
tics of waters necessary to support designated uses. State criteria are normally based on federal water
quality criteria, which have been published for more than 150 pollutants. The EPA published a com-
pilation of its criteria for 157 pollutants in 1998 (Fed. Reg., 63, 67547, 7 December 1998). Normally,
a state water quality standard consists of a numeric level of a pollutant that cannot be exceeded in the
ambient water in order to protect the designated use. For example, the standard may state that the
level of arsenic in a stream designated for trout propagation may not exceed 0.2 mg/l.
4.3.2 EPA PRIORITY TOXIC POLLUTANTS

According to the Federal Pollution Control Act, the EPA should study particular chemical com-
pounds and classes of compounds for the development of regulations to control discharges into
wastewater, using the BAT that is financially viable. Of these 129 priority pollutant compounds, 114
are organic and 15 inorganic. Metals account for 13 of the 15 inorganic pollutants (see Table 4.2).
4.4 AGRICULTURALLY USED WATERS

Water used for irrigation should be free from high salinity and toxic substances. Table 4.3 presents
the list of analytical parameters necessary to evaluate irrigation water quality. Of particular interest
is the ratio of sodium to calcium and magnesium. When sodium-rich water is applied to soil, some
of the sodium is taken up by clay and the clay gives up calcium and magnesium in exchange. Clay
that takes up sodium becomes sticky and slick when wet and has low permeability. The dry clay
shrinks into hard clods that are difficult to cultivate. In other words, when sodium is absorbed into
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TABLE 4.2
Priority Toxic Pollutants
Halogenated methanes 2,4-Dinitrophenol

Methyl bromide 4,6-Dinitro-o-cresol
Methyl chloride Chlorophenols
Methylene chloride (dichloromethane) 2-Chlorophenol
Bromoform (tribromomethane) 4-Chloro-m-cresol
Chloroform (trichloromethene) 2,4-Dichlorophenol
Bromodichloromethane 2,4,6-Trichlorophenol
Chlorodibromomethane Pentachlorophenol
Carbon tetrachloride (tetrachloromethane) 2,3,7,8-Tetrachlorodibenzol-p-dioxin (TCDD)
Chlorinated hydrocarbons Benzidines, hydrazine

Chloroethane (ethyl chloride) Benzidine
Chloroethylene (vinyl chloride) 3,3-Dichlorobenzidine
1,2-Dichloroethane (ethylenedichloride) 1,2-Diphenylhydrazine
1,1-Dichloroethane
1,2-trans-Dichloroethylene Phtalate esters
1,1-Dichloroethylene (vinylidene chloride) bis-(2-Ethylhexyl) phtalate
1,1,2-Trichloroethane Butylbenzyl phtalate
1,1,1-Trichloroethane Di-n-butyl phtalate
Trichloroethylene Di-n-octyl phtalate
Tetrachloroethylene Diethyl phtalate
1,1,2,2-Tetrachloroethane Dimethyl phtalate
Hexachloroethane
1,2-Dichloropropane Aromatics
1,3-Dichloropropylene Benzene
Hexachlorobutadiene Toluene
Hexachlorocyclopentadiene Ethylbenzene
Chloroalkyl ethers Polyaromatics

bis-(2-Chloroethyl) ether Naphthalene
bis (2-Chloroisopropyl) ether Acenaphthene
2-Chloroethylvinyl ether Acenaphthylene
bis-(2-Chloroethoxy) methane Anthracene
Benzo(a)anthracene (1,2-benzanthracene)
Haloaryl ethers Benzo(a)pyrene (3,4-benzopyrene)
4-Chlorophenyl phenyl ether 3,4-Benzofluoranthene (11,12-benzofluoranthene)
4-Bromophenyl phenyl ether Benzo(ghi)perylene (1,12-benzoperylene)
Chrysene
Nitrosamines Dibenzo(a,h)anthracene (1,2,5,6-dibenzoanthracene)
N-nitrosodimethyl amine Fluorene
N-nitrosodiphenyl amine Fluoranthene
N-nitrosodi-n-propyl amine Indenol(1,2,3-od)pyrene (2,3-o-phenylene pyrene)
Phenanthrene
Nitroaromatics Pyrene
Nitrobenzene
2,4-Dinitrotoluene Chloroaromatics
2,6-Dinitrotoluene Chlorobenzene
o-Dichlorobenzene
Phenols p-Dichlorobenzene
2,4-Dimeethylphenol m-Dichlorobenzene
1,2,4-Trichlorobenzene
Nitrophenols
Hexachlorobenzene
2-Nitrophenol
2-Chloronaphthalene
4-Nitrophenol
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TABLE 4.2 (Continued)

Polychlorinated Biphenyls (PCBs) Miscellaneous
PCB-1016 (Aroclor 1016) Acrolein
PCB-1221 (Aroclor 1221) Acrylonitrile
PCB-1232 (Aroclor 1232) Isophorone
PCB-1242 (Aroclor 1242) Asbestos
PCB-1248 (Aroclor 1248) Cyanide
PCB-1284 (Aroclor 1284) Metals
PCB-1260 (Aroclor 1260) Antimony
Arsenic
Pesticides Beryllium
Aldrin Cadmium
Dieldrin Chromium
Chlordane Copper
α-Endosulfate Lead
Endrin Mercury
Endrin aldehyde Nickel
Heptachlor Selenium
Heptachlor epoxide Silver
α-BHC Thallium
β-BHC Zinc
γ-BHC
δ-BHC
4,4-DDT
4,4-DDE (p,p-DDX)
4,4-DDO (p,p-TDE)
Toxaphene
clay particles, it turns the clay into a cement-like solid that neither water nor roots can penetrate. High
concentrations of sodium salts can produce alkali soils in which little or no vegetation can grow. On
the other hand, when the same clay carries excess calcium and magnesium ions, it tills easily and has
good permeability. If irrigation water contains calcium and magnesium ions sufficient to equal or
exceed the sodium ion, enough calcium and magnesium are retained in clay particles to maintain
good tilth and permeability.
The sodium effect can be calculated by the sodium absorption ratio (SAR) method:
SAR = [Na]/([Ca] + [Mg])/2 (4.1)
where the [Na], [Ca], and [Mg] values are expressed in milliequivalents per liter.
Waters with SAR values below 10 are acceptable for irrigation, and waters with SAR values of
18 or higher are not recommended for irrigation. Table 4.3 contains the recommended maximum
concentrations of trace elements in irrigation water.
4.5 INDUSTRIAL WATERS

Quality requirements for industrial use vary widely according to potential use. Industrial process wa-
ters must be of much higher quality than cooling waters (especially if they are used only once).
Municipal supplies are generally good enough to satisfy the quality requirements of most process
waters, with the exception of waters used for boilers. Boiler waters are specially checked and treated
for quality. Silica is an important constituent of the encrusting material or scale formed by many
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TABLE 4.3
Recommended Maximum Concentrations of Trace Elements in Irrigation Water
For Waters Continuously For Waters Used up to 20 Years

Used on Soils on Fine-Textured Soils, pH 6.0–8.5
(mg/l) (mg/l)
Aluminum (Al) 5.00 20.00

Arsenic (As) 0.10 2.00
Beryllium (Be) 0.10 0.50
a
Boron (B) 2.00
Cadmium (Cd) 0.01 0.05
Chromium (Cr) 0.10 1.00
Cobalt (Co) 0.05 5.00
Copper (Cu) 0.20 5.00
Fluoride (F) 1.00 15.00
Iron (Fe) 5.00 20.00
Lead (Pb) 5.00 10.00
Lithium (Li) 2.50 2.50
Manganese (Mn) 0.20 10.00
Molybdenum (Mo) 0.01 0.05b
Nickel (Ni) 0.20 2.00
Selenium (Se) 0.02 0.02
Vanadium (V) 0.10 1.00
Zinc (Zn) 2.00 10.00
a
No problem <0.75 mg/l; increasing problem, 0.75–2.00 mg/l; severe problem, >2.00 mg/l.
b
Only for acidic, fine-textured soils with relatively high iron oxide content.
Source: National Academy of Sciences and National Academy of Engineering, 1972; Driscoll, F.G., Groundwater and
Wells, 2nd ed., Johnson Division, St. Paul, MN, 1987. With permission.
waters. As a deposit, the scale commonly consists of calcium or magnesium silicate. Silicate scale
cannot be dissolved by acids or other chemicals. Therefore, silica-rich water used in boilers must be
treated. Sanitary requirements for waters used in processing milk, canned goods, meats, and bever-
ages exceed even those in drinking water.
4.6 WASTE CHARACTERIZATION

The few characteristic properties that qualify waste material under the Resource Conservation and
Recovery Act (see Section 4.3.1) are ignitability, corrosivity, reactivity, and toxicity.
Ignitability: This property refers to the characteristics of being able to sustain combustion, in-
cluding flammability (ability to start fires when heated to temperatures of less than 60°C or
140°F).
Corrosivity: Corrosive wastes may destroy containers, soil, and ground water or react with
other materials to cause toxic gas emissions. Corrosive materials provide a very specific
hazard to human tissue and aquatic life when pH levels are extreme.
Reactivity: Reactive wastes may be unstable or have a tendency to react, explode, or generate
pressure during handling. Pressure-sensitive or water-reactive materials are also included in
this category.
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Toxicity: Toxicity is an effect of waste materials that may come into contact with water or air
and be leached into groundwater or dispersed in the environment. Toxic effects on humans,
fish, or wildlife are the principal concerns.
4.7 HAZARDOUS WASTE CHARACTERIZATION

The Resource Conservation and Recovery Act (RCRA) and its amendment, the Hazardous and Solid
Waste Act, deal with management of solid wastes with an emphasis on hazardous wastes. The goal
of the RCRA program is to regulate all aspects of hazardous waste management, from production
through treatment and disposal. These wastes include toxic substances, caustics, pesticides, and
flammable, corrosive, and explosive materials.
4.7.1 CRITERIA FOR HAZARDOUS WASTE EVALUATION

The criteria for evaluating hazardous waste are as follows:
Ignitability: Flashpoint less than 60°C (less than 140°F)

Corrosivity: pH less than 2.00 or higher than 12.00
Reactivity: Reacts violently or generates pressure; the substance should be free from cyanide
(CN) and sulfide (S)
Toxicity: Leaching test — extraction procedure toxicity (EPTOX) and toxicity characteristic
leachate procedure (TCLP) — parameters should meet MCLs
TABLE 4.4
Maximum Concentration of Contaminants in Characterization
of EP Toxicity
Contaminant Maximum Concentration (mg/l)

Arsenic (As) 5.0
Barium (Ba) 100.0
Cadmium (Cd) 1.0
Chromium (Cr) 5.0
Lead (Pb) 5.0
Mercury (Hg) 0.2
Selenium (Se) 1.0
Silver (Ag) 5.0
Endrin 0.02
Lindane 0.4
Methoxychlor 10.0
Toxaphene 0.5
2,4-D 10.0
2,4,5-TP Silvex 1.0
Note: The EP toxicity test (EPTOX) was developed to characterize hazardous wastes based
on the leaching ability of toxic substances in significant concentrations. 2,4-D = 2,4-
Dichlorophenoxyacetic acid; 2,4,5-TP = 2,4,5-trichlorophenoxyacetic acid; EP toxicity =
extraction procedure toxicity.
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The characterization of hazardous wastes is based on their leaching ability of toxic substances in
significant concentrations. In the EPTOX test, the liquid extract or leachate of the material is ana-
lyzed for 14 parameters: 8 metals, 4 insecticides, and 2 herbicides. During the migration of the
leachate, attenuation and dilution occur with the ratio factor of 100, which is used to establish the
maximum concentration level (100 times higher than drinking water standards). Maximum concen-
trations of contaminants in EPTOX leachate are presented in Table 4.4. The EPA developed the
EPTOX test in 1980 (40 CFR, 261.24). (The EPTOX procedure is discussed in Chapter 14.)
In 1986, the EPA expanded the EPTOX characteristic substances by adding 38 organic pollu-
tants. The new procedure is called the toxicity characteristic leachate procedure (TCLP). By the ap-
plication of the TCLP test, the leachate of the waste material containing any of these 52 substances
at or above the regulatory level qualifies as hazardous, toxic waste. The TCLP test uses compound-
specific dilution/attenuation factors instead of the 100 used in the EPTOX test. The extraction pro-
cedure is the same as specified for the EPTOX test. Contaminants and regulatory levels are list in
Table 4.5.
4.8 AIR POLLUTION AND CONTROL

4.8.1 PRIMARY AND SECONDARY AIR POLLUTANTS
People have known for centuries that air carries “poisons.” Coal miners used to take canaries with
them into the mine because the death of a bird meant the presence of toxic gases. An important ex-
posure route to hazardous materials is air, and the effects of airborne hazardous materials frequently
appear at a great distance from pollution sources. The atmosphere contains hundreds of air pollutants
from natural and anthropogenic sources, known as primary pollutants. By using the energy from the
sun, primary pollutants react with one another or with water vapor in the air and produce dangerous
new chemical substances called secondary pollutants. These reactions are called photochemical reac-
tions because they involve sunlight and chemicals, resulting in a brownish-orange shroud of air pollu-
tion called photochemical smog. Secondary pollutants include ozone, formaldehyde, peroxyacylni-
trate, sulfuric acid, and nitric acid (causes of acid rain). Acute health effects include burning or itch-
ing eyes and irritated throats, and chronic effects include bronchitis, emphysema, and lung cancer.
4.8.2 CLEAN AIR ACT (CAA)

Air pollution control began in 1955. However, the Clean Air Act of 1970 (amended in 1975 and 1977)
marked the beginning of attempts at effective controls. The two broad regulatory classifications of air
pollutants are criteria and noncriteria pollutants.
4.8.2.1 Criteria Pollutants

Federal ambient air quality standards have been established for criteria pollutants, which include
gases in the form of nitrogen oxides, ozone, sulfur dioxide, carbon monoxide, and solids in the form
of particulate matter and lead (as particulates).
4.8.2.2 Noncriteria Pollutants

Federal ambient air quality standards have not been established for noncriteria pollutants (toxic air
contaminants), which include practically every other compound or element that could have an impact
on human health or the environment.
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TABLE 4.5
Toxic Characteristic Leachate Pollutants (TCLPs) and Regulatory Levels
Contaminant Regulatory Level (mg/l)
Organics
Acrylonitrile 5.0
Benzene 0.07
bis-(2-Chloroethyl) ether 0.05
Carbon disulfide 0.07
Carbon tetrachloride 0.03
Chlordane 0.03
Chlorobenzene 1.4
Chloroform 0.07
o-Cresol 10.0
m-Cresol 10.0
p-Cresol 10.0
2,4-D 1.4
1,2-Dichlorobenzene 4.3
1,4-Dichlorobenzene 10.8
1,2-Dichloroethane 0.40
1,3-Dichloroethylene 0.10
2,4-Dinitritoluene 0.13
Endrin 0.003
Heptachlor (and its hydroxide) 0.001
Hexachlorobenzene 0.13
Hexachlorobutadiene 0.72
Hexachloroethane 4.3
Isobutanol 36.0
Lindane 0.06
Methoxychlor 1.4
Methylene chloride 6.6
Methyl ethyl ketone 7.2
Nitrobenzene 0.13
Pentachlorophenol 3.6
Phenol 14.4
Pyridine 5.0
1,1,1,2-Tetrachloroethane 10.0
1,1,2,2-Tetrachloroethane 1.3
Tetrachloroethylene 0.1
2,3,4,6-Tetrachlorophenol 1.5
Toluene 14.4
Toxaphene 0.07
1,1,1-Trichloroethane 30.0
1,1,2-Trichloroethane 1.2
Trichloroethylene 0.07
2,4,5-Trichlorophenol 5.8
2,4,6-Trichlorophenol 0.30
2,4,5-TP (Silvex) 0.14
Vinyl chloride 0.05
Metals
Arsenic (As) 5.0
Barium (Ba) 100.0
Cadmium (Cd) 1.0
Chromium (Cr) 5.0
Lead (Pb) 5.0
Mercury (Hg) 0.2
Selenium (Se) 1.0
Silver (Ag) 5.0
Note: In 1986, the EPA expanded the EP toxicity characteristic substances (Table 4.3), which included 8 metals, 4 insecti-
cides, and 2 herbicides, to encompass an additional 38 organic substances. The new procedure is called the toxic character-
istic leachate procedure (TCLP) test. Through the application of the TCLP test, the extract or leachate of the waste contain-
ing any of these 52 substances at or above the regulatory level qualifies as hazardous toxic waste.
Sources: For parameters and regulatory levels, see U.S. Environmental Protection Agency, “Hazardous Waste Management
System,” 51 CFR, 114, 13 June 1986. For updated TCLP procedure, see 51 CFR, 114, 13 June 1986. For earlier version, see
40 CFR, 261.24, 19 May 1980.
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4.8.2.3 Air Quality Regulations

In October 1966, the EPA issued its decision not to set a short-term National Ambient Air Quality
Standard (NAAQS) for NO2 (Fed. Reg., 61, 52852, 1996).
More important, on May 22, 1996, the EPA promulgated a decision not to tighten the NAAQS
for SO2 (Fed. Reg., 61, 25566, 1996). This decision followed an EPA proposal dated November 1994
to revise the SO2 ambient standard to include a 0.06-ppm, 5-min average standard. Instead of tight-
ening the NAAQS for SO2, on January 2, 1997, the EPA proposed a program for monitoring and reg-
ulation of the 5-min average peak SO2 concentration in the “emergency powers” provision. On
January 30, 1998, in response to a petition from the American Lung Association, the D.C. Circuit
Court set aside the EPA’s decision on the NAAQS for SO2 as inadequately justified.
In 1997, the EPA issued proposed rules substantially tightening the NAAQS for particulate mat-
ter (PM) and ozone (see Fed. Reg., 62, 38856, 1997, for ozone; Fed. Reg., 62, 38652, 1997, for PM).
The EPA’s PM rules addressed fine particles of 2.5 microns or less (i.e., PM-2.5) and contain an an-
nual standard of 15 µg/m3 (mean) and a 24-h standard of 65 µg/m3.
The PM-2.5 standards would result in many new nonattainment areas. Because gaseous emis-
sions react in the atmosphere to form PM-2.5, these new standards established new, more stringent
sulfur dioxide (SO2), nitrogen oxide (NOx), and volatile organic compound (VOC) emission controls
for many industries.
At the same time it promulgated the PM-2.5 standard, the EPA also proposed a new, more strin-
gent NAAQS for ozone of 0.08 ppm, using an 8-h average, with compliance determined on the basis
of the third-highest reading. In addition, the EPA issued a new secondary NAAQS for ozone at the
same level as the primary NAAQS.
The Clean Air Act gives each state primary responsibility for ensuring that emissions from
sources within its borders (including emissions that remain within and travel beyond state borders)
are maintained at a level consistent with the NAAQS. This is achieved through the establishment of
source-specific requirements in state implementation plans that address primary and secondary air
quality standards.
4.8.2.4 Specific Noncriteria Standards

Under the 1990 amendments, ozone nonattainment areas are designated as marginal, moderate, seri-
ous, severe, or extreme, depending on the severity of the problem. Marginal areas are required to at-
tain the ozone NAAQS within 3 years of enactment of the 1990 amendments, moderate areas within
6 years, serious areas within 9 years, severe areas within 15 years (in some cases, 17 years), and ex-
treme areas within 20 years. CO nonattainment areas are designated as either moderate or serious.
Moderate areas had to attain the CO standard by 1995, and serious areas by 2000. Under the 1990
amendments, all PM-10 areas initially were classified as moderate. Serious PM-10 areas were given
until 2001 to attain the standard.
4.8.3 AMBIENT AIR QUALITY STANDARD (AAQS)

This standard addresses contaminant levels above which adverse health effects occur. Air pollution
regulation is focused on pollutant sources. Air pollution sources are classified as follows:
1. Mobile sources, including engines, usually associated with transportation (e.g., automo-
biles, airplanes, trucks, trains, and ships)
2. Stationary sources, such as pipelines, factories, boilers, storage vessels, and storage tanks;
these sources are classified as point sources (e.g., chimneys) and area sources (e.g., park-
ing lots and industrial facilities)
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The federal government has primary authority to regulate emissions from mobile sources.
Regulations for automobile emission controls have become more stringent as increasingly effective
technologies emerge. The use of catalytic converters and unleaded gasoline has been a great step for-
ward in the development of better air quality.
To regulate stationary sources, the EPA sets national stationary standards, known as the new
source performance standards. The federal government adopts these emission standards on an
industry-specific basis for all new sources of air-contaminant-emitting equipment or processes
located anywhere in the United States. Local authorities under the jurisdiction of the respective
state control these standards. The inspection and maintenance of vehicles for air emissions are also
regulated by state laws.
4.9 ISO 14001 AND ENVIRONMENTAL LAW

4.9.1 ENVIRONMENTAL MANAGEMENT SYSTEMS (EMSS)
Environmental management systems (EMSs) are applications of well-accepted business principles to
environmental protection. EMSs identify key issues, establish what to do (policy and objectives), de-
termine how to do it (programs, procedures, and instructions), tell people what to do (communica-
tion and training), make sure they do it (implementation, measurement, and auditing), and periodi-
cally review the entire process to identify opportunities for improvement. EMSs focus on establish-
ing programs and procedures to integrate environmental performance into everyday operations so
that organizations “do it right the first time.”
4.9.2 ISO 14001 EMS STANDARD

ISO 14001, a voluntary, comprehensive EMS standard published by the International Organization
on Standards in late 1999, is intended to assist organizations in identifying and meeting their envi-
ronmental obligations and commitments. The popularity of EMSs is reflected in the rapid and wide-
spread acceptance of ISO 14001. By mid-2000, over 15,000 organizations worldwide had imple-
mented EMSs that were third-party certified as conforming to the ISO 14001 EMS standard, and
countless other organizations have been using the standard. Nearly 1000 organizations in the United
States have already been certified as conforming to ISO 14001, and this number is expected to in-
crease dramatically.
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Fundamentals of Spectroscopy
5
5.1 EARLY HISTORY OF THE NATURE OF LIGHT
For millennia, people have been curious about the nature of light, and particularly of color. From the
time of the ancient Greeks to the seventeenth century, scholars and others believed that colors con-
sisted of a mixture of white light and darkness and could be changed by changing the mixture.
This view was radically changed by the work of Isaac Newton (1642–1727). At the age of 24, he
began his research on light. In a well-known experiment, a ray of sunlight was passed through a hole
into a darkened room and onto a screen. A prism, placed in the beam of the light, dispersed the light
into a spectrum of colors in the order red, yellow, green, blue, and violet. Newton concluded that
white light is a “confused aggregate of rays imbued with all sort of colors.” The function of the prism
was merely to separate the light into its component colors.
No more discoveries occurred until 1800, when British astronomer William Herschel discovered
the infrared portion of the solar spectrum. Soon after, the ultraviolet part of the spectrum was identified.
In 1802, scientists reported dark lines in the sun’s spectrum, but could not provide a satisfactory
explanation. In 1817, Joseph Fraunhofer, an optician and instrument maker, noted the same lines.
With improved equipment, he proceeded to map the dark lines of the solar spectrum, and calculated
the corresponding wavelengths. Still known as Fraunhofer lines, this phenomenon is described as
“dark lines in the solar spectrum that result from the absorption by elements in the solar chromos-
phere of some of the wavelengths of the visible radiation emitted by the hot interior of the sun” (A
Concise Dictionary of Chemistry, 1990, p. 127). During the late eighteenth and early nineteenth cen-
turies, Fraunhofer and others looked at spectra emitted by flames and sparks, and compared them to
the spectra emitted by the sun.
During the first half of the nineteenth century, a good deal of experimentation took place with the
colored flames produced by injecting various salts into a flame. When light was passed through a slit
and prism onto a screen, bright discrete lines were seen against a dark background, the reverse of the
solar spectrum. The connection between the two was not made for many years. Robert Bunsen, pro-
fessor of chemistry at the University of Heidelberg (designer of the Bunsen gas burner), viewed the
exhibited colored flames by different salts through a spectroscope. He noted that the colors were
linked to the element, not the compound in which it was bound. He realized that the bright lines in
the visible region of the spectrum seen with a spectroscope were characteristic of specific elements,
and that the method could be used as an extremely sensitive and simple method of element identifi-
cation. With this new method, Bunsen identified and isolated two new elements, cesium (Cs) and ru-
bidium (Rb).
Gustav Kirchhoff, a professor of physics at Heidelberg University, became interested in Bunsen’s
work. Kirchhoff examined the dark lines of the spectrum and concluded that the appearance of these
lines are due to a process of absorption as the emission rays pass through the cool outer layer of the
sun’s atmosphere, which causes them to show up dark against the bright background. This phenom-
enon, called the absorption spectrum, is just as characteristic of a specific element as its emission
spectrum. The effectiveness of Bunsen and Kirchhoff’s spectroscopy in chemical analysis was first
79
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used as a qualitative method. Modern quantitative methods did not emerge until about the 1920s,
when suitable commercial optical equipment began to appear. The method used at this time was
emission spectroscopy.
In 1939, Woodson was the first to apply the absorption procedure in the quantitative measure-
ment of elements when he identified characteristics of mercury. Atomic absorption spectroscopy was
born in 1955, when two independently published papers described the method.
5.2 ELECTROMAGNETIC RADIATION

One of the ways that energy travels through space is electromagnetic radiation. The light from the
sun, the energy used for cooking food in a microwave oven, the x-rays used in the medical field, and
the radiant heat from a fireplace are all examples of electromagnetic radiation. Although these forms
of radiant energy seem quite different, they all exhibit the same type of wavelike behavior and travel
at the speed of light in a vacuum. Waves have three primary characteristics: wavelength, frequency,
and speed.
Wavelength (symbolized by the Greek letter lambda, λ) is the distance between two consecutive
peaks of the wave as shown in Figure 5.1. The frequency (symbolized by the Greek letter nu, ν) is
defined as the number of waves (cycles) per second that pass a given point in space. Because all types
of electromagnetic radiation travel at the speed of light, short-wavelength radiation must have a high
frequency. This implies an inverse relationship between wavelength and frequency:
λν = c (5.1)
where
λ = wavelength in meters.
mν = frequency in cycles per second in Hz (1/sec or sec–1).
c = speed of light (2.9979 × 108 m/sec).
Electromagnetic radiation is classified by wavelength range, as illustrated in Figure 5.2. Each

portion of the spectrum has a popular name. For example, radio waves are electromagnetic radia-
tion with low frequencies and therefore very long wavelengths. Microwaves also have low frequen-
cies and are emitted by radar instruments. Microwaves are absorbed by molecules in food, and the
energy the molecules take on raises their temperature. This is why foods cook quickly in a
1 second
λ1
ν1 = 4 cycles/second = 4 hertz
λ2
ν2 = 8 cycles/second = 8 hertz
λ3
FIGURE 5.1 The nature of waves. Note that the radiation

ν3 = 16 cycles/second = 16 hertz with the shortest wavelength has the highest frequency.
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Fundamentals of Spectroscopy 81
Microwaves
1000 µm
100 µm
Far infrared
10 µm (750 nm)
Wavelength Red
Near infrared Orange
(1 µm) 1000 nm Yellow
Visible
Green
Near ultraviolet
100 nm Blue
Vacuum ultraviolet Violet
(380 nm)
10 nm
X-rays
X-rays
Gamma rays
FIGURE 5.2 Electromagnetic radiation.
microwave oven. Infrared radiation is emitted by hot objects and consists of the range of frequen-
cies that can make molecules of most substances vibrate internally. Infrared radiation is not visible,
but how the body absorbs it can be felt by holding out a hand near a hot radiator; the absorbed ra-
diation warms the hand.
Each substance absorbs a uniquely different set of infrared frequencies. A plot of frequencies ab-
sorbed vs. the intensities of absorption is called an infrared absorption spectrum. It can be used to
identify a compound, because each infrared spectrum is as unique as a fingerprint. Gamma rays are
at the high-frequency end of the electromagnetic spectrum and are produced by some radioactive el-
ements. X-rays are much like gamma rays, but they are usually made by special equipment. Both x-
rays and gamma rays easily penetrate living organisms.
Human eyes are able to sense only a narrow band of wavelengths, ranging from about 400 to 700
nm. This band is called the visible spectrum and consists of all the colors we can see, from red
through orange, yellow, green, blue, and violet. White light is composed of all these colors in roughly
equal amounts, and it can be separated into them by focusing a beam of white light through a prism,
which spreads the various wavelengths apart. Table 5.1 contains the wavelength region of each color.
5.2.1 The Dual Nature of Light

In 1901, German physicist Max Planck proposed that electromagnetic radiation is emitted only in
tiny packets or quanta of energy, which later became known as photons. The energy of one photon is
called one quantum of energy.
E = hν (5.2)
where
E = the energy of a photon.
h = Planck’s constant.
ν = frequency of the electromagnetic radiation absorbed or emitted.
The value of h is 6.626 × 10–34 J (units of energy, Joules) multiplied by time (seconds). Each pho-
ton pulses at a frequency and travels at the speed of light. Planck proposed and Albert Einstein
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TABLE 5.1
Wavelength Regions by Color
Wavelength Region (nm) Color
380–450 Violet
450–495 Blue
495–550 Green-yellow
550–570 Green
570–590 Yellow
590–620 Orange
620–750 Red-purplea
a
Purple is visible when equal numbers of photons of blue and red light
strike the eye.
(1879–1955) confirmed that the energy of a photon of electromagnetic radiation is proportional to its
frequency. According to Einstein’s famous equations,
E = mc2 (5.3)
m = E/c2 (5.4)
where
E = energy.
m = mass.
c = the speed of light.
The main significance of this equation is that energy has mass. We can summarize the conclusions
of Planck and Einstein’s work as follows:
1. Energy is quantized and can occur in discrete units or quanta.

2. Electromagnetic radiation, which was previously believed to exhibit only wave properties,
was found to have certain characteristics of particulate matter. Hence, scientists became
aware of the dual nature of light.
5.3 CONTINUOUS AND LINE SPECTRA

5.3.1 CONTINUOUS SPECTRUM
When the light from the sun or from an object heated to a very high temperature (such as a light bulb
filament) is split by a prism and displayed on a screen, a continuous spectrum forms. The spectrum
contains light of all colors, as seen in Figure 5.3. A rainbow seen after a summer shower is a contin-
uous spectrum. In this case, the colors contained in the sunlight are spread out by tiny water droplets
in the air. The water droplets act as a prism.
In molecular absorption, both electronic and vibrational transitions are possible, because all
wavelengths have a chance of being absorbed to some degree. The result is a continuous spectrum.
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Continuous
spectrum
VIBG
(+) YOR
(-)
Electric arc Slit Prism Detector
(white light source) (photographic plate)
(a)
410 nm
434 nm
486 nm
656 nm
High
voltage Detector
(photographic plate)
Hydrogen Slit Prism

gas Arc
(b)
FIGURE 5.3 (a) Continuous spectrum obtaining all wavelengths of visible light (indicated by the initial letters
of the colors of the rainbow). (b) The hydrogen line contains only a few discrete wavelengths.
5.3.2 LINE SPECTRUM

When a light given off by an electrical discharge passes through a gas and is separated by a prism, a
rather different spectrum can be observed on the screen. The discharge in an electrical current excites
or energizes the atoms of the gas. The atoms absorb the energy, electrons are promoted to higher en-
ergy levels, and the electrons emit the absorbed energy in the form of light when they return to the
lower energy state. When a narrow beam of this light is passed through a prism, only a few colors are
observed as a series of discrete lines. This line spectrum is illustrated in Figure 5.3.
Atoms have no vibrational energy transition and all energy transfer is electronic. A limited num-
ber of wavelengths are absorbed, and only those wavelengths show up in the spectrum. The result is
a line spectrum.
5.4 ABSORPTION AND EMISSION

According to the Bohr model of an atom, the nucleus is surrounded by electrons that travel around it
in discrete orbitals. Every atom has a number of orbitals in which it is possible for electrons to travel.
Each of these electron orbitals has an energy level associated with it; in general, the farther away from
the nucleus an orbital is, the higher its energy level.
When the electrons of an atom are closest to the nucleus and lowest in energy, the atom is in its most
stable state, known as ground state. With the addition of sufficient energy to atoms, electrons can be
promoted from a lower energy level to a higher, vacant energy level. When light strikes an electron,
causing it to be promoted to a higher energy level, the electron now possesses the energy that once was
light. This is a less stable configuration, called the excited state. An important point concerning the
L1572_C05 5/23/02 1:22 PM Page 84
process, however, is that the light coming through must be exactly the same energy as the energy dif-
ference between the two energy levels; otherwise, the light will not be absorbed. The atom is less sta-
ble in its excited state and will thus decay back to a less excited state by losing energy through collision
with another particle or by emission of a “particle” of light (electromagnetic radiation), known as a pho-
ton. The electron will return to its initial, stable orbital position, and radiant energy equivalent to the
amount of energy absorbed in the excitation process will be emitted. The excitation is forced by sup-
plying energy, but the decay, involving the emission of light, occurs spontaneously.
Because only certain energy jumps can occur, only certain colors can appear in the spectrum.
Figure 5.4 illustrates this electronic energy transfer. For analytical purposes, either the energy ab-
sorbed in the excitation process or the energy emitted in the decay process can be measured.
Every element has a characteristic set of energy levels and thus a unique set of absorption and
emission wavelengths. This property makes atomic spectrometry useful in element-specific analyti-
cal techniques. If light of the correct wavelength reaches a ground-state atom, the atom absorbs the
light and enters into the excited state, and the quantity of the absorbance is measured via atomic ab-
sorption spectrophotometry. In atomic emissions, the sample is placed in a high-thermal-energy en-
vironment, the atoms of the sample are excited, and light is emitted. The intensity of the emitted light
is measured via atomic emission spectrophotometry.
The other form of interaction between energy and electrons is vibrational energy. Vibration re-
quires less energy.
5.4.1 MOLECULAR VS. ATOMIC SPECTRA

The measurement of the absorption and emission of light can be more easily described when the
atomic and molecular spectra are understood. The absorption of light by individual, nonbonded
atoms must be considered separately from molecular absorption.
5.4.1.1 Atomic Spectrum

To produce an atomic spectrum, a compound must first absorb enough energy to vaporize it into a
molecular gas and dissociate the molecules into free atoms. In atoms, all energy transitions are elec-
tronic; therefore, only individual, discrete, electronic transitions are possible. Each discrete energy
increase is due to the absorption of the wavelength corresponding to that energy. Consequently, only
those wavelengths are absorbed, and only those wavelengths show up in the atomic spectrum or line
spectrum (see Figure 5.3).
Atomic spectra are produced as follows:
Atomic absorption spectra are produced when the free atoms absorb radiant energy at charac-
teristic wavelengths.
Atomic emission spectra are produced when the free atoms are excited by the thermal energy
of a flame, arc, spark, or plasma and emit radiant energy at similar wavelengths.
EXCITATION DECAY
λ
(1) Energy + (2) +
Ground Excited Excited Ground Light
State State State State Energy
Atom Atom Atom Atom
FIGURE 5.4 Electronic energy transition. Step (1), excitation, is forced by supplying energy. The decay
process in step (2), involving the emission of light, occurs spontaneously. Because every element has a unique
electronic structure, the wavelength of light emitted is a unique property of each individual element.
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5.4.1.2 Molecular Absorption

In molecular absorption, electronic and vibrational transitions are possible; therefore, a large num-
ber of wavelengths are absorbed and produce a continuous spectrum (see Section 5.3.1). Because the
amount of light absorbed by a sample is proportional to the concentration of the absorbing species
(Beer’s law; see Section 5.5), light absorption can be used as an analytical technique in quantitative
analytical chemistry. The instrument used for measurement of absorption is the spectrophotometer.
Molecular spectrophotometry (used in the UV/Vis and IR regions) and its operational techniques are
discussed in detail in Chapter 6.
5.5 BEER’S LAW

The amount of light absorbed by a sample is proportional to the concentration of the absorbing
species in the sample. There is, then, a linear relationship between absorbance and concentration.
This relationship is well defined in the Beer–Lambert law (known simply as Beer’s law): The amount
of light absorbed or transmitted by a solution is a function of concentration of the substance and the
sample path length. The formula follows:
A = abc (5.5)
where
A = absorbance.
a = absorptivity (sometimes called an extinction coefficient), the ability of the
absorbing species to absorb light. Absorptivity depends on the electronic and
vibrational transitions in a given species. The numerical value of a depends
on the units used for expressing the concentration of the absorbing solution.
b = diameter, or width of the cuvette, called pathlength. A wider cuvette has more
of the absorbing species and therefore results in greater absorbance.
c = concentration.
For example, assume that a 2.00 ppm (parts per million = mg/l) standard measured in a 1-cm cu-
vette shows absorbance of 0.246. What is the concentration of a sample, if the measured absorbance
is 0.529 and it is also measured in a 1-cm cuvette?
c1 = 2.00 ppm
c2 = ?
b1 = 1 cm
b2 = 1 cm
A1 = 0.246
A2 = 0.529
a=?
Using Beer’s law, to calculate the sample concentration, with knowledge of the absorbance and
the path length, we need the value of the absorptivity of the species. Based on knowledge of the val-
ues of the analyzed standard, we are able to calculate the numerical expression of the absorptivity:
A1 = a × b1 × c1 (5.6)
0.246 = a × 1 × 2
a = 2/0.246
a = 0.123
A2 = a × b2 × c2
0.529 = 0.123 × 1 × c2
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FIGURE 5.5 Atomic spectroscopy systems.
c2 = 0.529/0.123
c2 = 4.3 ppm
5.6 ATOMIC SPECTROSCOPY TECHNIQUES

The most commonly used techniques for identifying trace concentrations of elements in samples are
based on atomic spectrometry. These techniques involve electromagnetic radiation (light) that is ab-
sorbed by or emitted from atoms of a sample. By using atomic spectroscopy techniques, meaningful
quantitative and qualitative information about the sample can be obtained. The qualitative informa-
tion is related to the wavelengths at which the radiation is absorbed or emitted, and the quantitative
information is related to the amount of electromagnetic radiation that is absorbed or emitted.
The sample is decomposed by intense heat into a cloud, or hot gases containing free atoms of the
elements of interest. Of the three techniques — atomic absorption, atomic emission, and atomic flu-
orescence — atomic absorption and atomic emission are the most widely used. Figure 5.5 illustrates
the arrangement of instruments in the three techniques. An understanding of atomic structure and of
the atomic process involved in each technique is necessary (see Section 5.4).
5.6.1 ATOMIC ABSORPTION SPECTROMETRY (AAS)

Light of a wavelength characteristic of the element of interest is beamed through the element’s
atomic vapor. The atoms absorb some of this light. The amount of light absorbed is measured and
used to determine the concentration of the element in the sample.
5.6.2 ATOMIC EMISSION SPECTROMETRY (AES)

The sample is subjected to temperatures high enough to cause not only dissociation into atoms, but
also significant amounts of collisional excitation (or ionization) of the sample atoms. Once the atoms
or ions are in their excitation states, they decay to lower states and energy is transmitted (see Section
5.4). The intensity of the light emitted at specific wavelengths is measured and used to determine the
concentration of the element of interest.
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5.6.3 ATOMIC FLUORESCENCE SPECTROMETRY (AFS)

This technique incorporates aspects of both atomic absorption and atomic emission. Like atomic ab-
sorption, ground-state atoms created in a flame are excited by focusing a beam of light into the atomic
vapor. Instead of measuring the amount of light absorbed in the process, the emission resulting from
the decay of the atoms excited is measured. The intensity of this “fluorescence” increases with atomic
concentration, providing the basis of quantitative determination. The source lamp for the AFS is
mounted at an angle to the rest of the optical system, so that the light detector sees only the fluores-
cence in the flame and not the light from the lamp itself.
5.6.4 ATOMIZATION PROCESS AND EXCITATION SOURCES

Three types of thermal sources are available to dissociate sample molecules into free atoms: flames,
furnaces, and electrical discharges. Flames and furnaces dissociate most types of molecules into free
atoms. Because most of the free atoms in typical flames and furnaces are in their ground states, AAS
is the preferred method to detect the presence of the element of interest.
Electrical discharges are used as atomization sources in AES. Arcs and sparks are electrical dis-
charges created by application of electrical currents or potentials across an electrode in an inert gas.
These discharges produce temperatures of about 7300°C. More recently, plasmas have been used as
atomization and excitation sources in AES. Plasma is any form of matter that contains electrons
(about 1%) and positive ions in the same quantity. The present state of the art in plasma sources for
AES is the argon-supported inductively coupled plasma (ICP). Other plasmas in use are the direct-
current plasma and microwave-induced plasma.
5.6.5 DEVELOPMENT OF ANALYTICAL TECHNIQUES

In the early twentieth century, the sharp lines that appeared in light emitted from electrical arcs and
sparks were used analytically for qualitative analysis. During the mid-twentieth century, quantitative
arc and spark spectroscopy was the best tool that analysts could use for the determination of trace con-
centrations of elements. While arc/spark emission techniques enjoyed widespread popularity for de-
termination of metals, flame emission spectrometry (also known as flame photometry) was used for
determination of alkalis and other easily excited elements. The most widespread use of the technique
is in clinical laboratories for determining sodium and potassium levels in blood and other biological
materials.
Flame emission spectrometry had the advantage of being simpler than arc/spark emission tech-
niques, but was also limited because flames were not hot enough to cause emission in many elements.
In the 1960s and 1970s, both flame and arc/spark atomic emission spectrometry declined in popu-
larity, and flame atomic absorption was mostly used to determine trace metals in solutions (solid
samples required dissolution prior to analysis). On the other hand, graphite furnace atomic absorp-
tion spectroscopy (GrAAS) was used when high-sensitivity and low-detection limits were needed.
However, the GrAAS technique is not as precise and is subject to more interference. Advances, such
as the stabilized temperature platform furnace technology and Zeeman background correction have
reduced or eliminated most interference. Both the flame and graphite-furnace AAS techniques are
used today and provide excellent means of trace element analysis. Most atomic absorption instru-
ments are limited to determining only one element at a time.
The first published report on using ICP for elemental analysis was issued in 1973. The obtained
law detection limits, freedom from interference, and long linear working ranges proved that it is a su-
perior technique for atomic emission analysis. Besides its ability to determine a large number of
elements over a wide range of concentrations, a major advantage of the ICP-AES technique is that
many elements can be determined easily in the same analytical run.
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Many laboratories are equipped with an ICP-AES instrument to perform moderate-sensitivity,

high-sample-throughput, multielement analyses and a graphite-furnace AAS instrument to perform
single-element determinations that require high sensitivity.
Inductively coupled plasma mass spectrometry (ICP-MS) is one of the most recently developed
techniques for trace element analysis. In this technique, the analyte ions formed in the ICP are sent
through a mass spectrometer where they are separated according to mass/charge (m/e) ratios. The
number of ions at ratios of interest are then measured and the results used for qualitative and quanti-
tative purposes. See Appendix A for more detail on MS.
5.6.6 COMPARISON OF TECHNIQUES USED IN TRACE ELEMENT ANALYSIS

5.6.6.1 Flame Atomic Absorption Spectrophotometry (FAAS)
The two principal advantages of FAAS are low initial cost and simplicity of operation.
5.6.6.2 Graphite Furnace Atomic Absorption Spectrophotometry (GrAAS)

The principal advantage of GrAAS over FAAS and ICP-AES is its greater sensitivity and lower de-
tection limits for most elements. A very small amount of sample can be easily analyzed with GrAAS.
5.6.6.3 Inductively Coupled Plasma Atomic Emission Spectrophotometry

(ICP-AES)
The main advantages of ICP-AES over AAS techniques in general are its multielement capabilities,
longer linear dynamic ranges, and fewer interferences.
5.6.6.4 Inductively Coupled Plasma Mass Spectrometry (ICP-MS)

A powerful technique for elemental analysis, ICP-MS has the sensitivity and detection limits typical of
GrAAS, combined with the multielement capability of ICP-AES. ICP-MS systems are expensive and
have severe sample–matrix interferences. Therefore, further development of the technique is limited.
5.6.6.5 Selecting a Technique

Because of the advantages and disadvantages of the various techniques, selecting one for a given cir-
cumstance is easy. If an application requires single-element analysis for relatively few samples or if ini-
tial cost is an important factor, then FAAS is a good choice. If an application requires very low detec-
tion limits for a few elements, use GrAAS. For applications involving multielement analyses from sam-
ples in a complicated matrix with moderate sensitivity, ICP-AES is a good choice. When an application
requires very low detection limits of many elements per sample, ICP-MS is the best technique.
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Molecular Spectrophotometry
6
As discussed in Chapter 5, the absorption properties of atoms and molecules are quite different. Light
absorption by individual, nonbonded atoms differs from that of molecules. Consequently, the tech-
niques and instrument designs differ significantly and must be discussed separately.
Absorption of light by molecules or ions causes two types of energy changes: electronic (change
in the energy of the electrons of a molecule) and vibrational (change in the internuclear distance of
two or more atoms in the molecule). Electronic transition requires more energy and thus occurs in
the visible–ultraviolet spectral region. Vibrational changes in a molecule result from the absorption
of low-energy infrared radiation.
6.1 MOLECULAR ABSORPTION AND COLOR

The color of a molecule in solution depends on the wavelengths of light it absorbs. Thus, when a sam-
ple solution of a molecule or ion is exposed to white light, certain wavelengths are absorbed, and the
remaining wavelengths are transmitted to the eye. The color perceived by the eye is determined only
by the wavelengths transmitted. The substance exhibits the color that is complementary to wave-
lengths absorbed. In simple terms, the color seen is the complementary color of the color absorbed.
Table 6.1 shows the general relationship between wavelengths of visible light absorbed and the color
observed. For example, if the color of the test solution is yellow, the selected wavelength should be
450 nm, and if the test solution is dark blue the absorbance measured is at the 580-nm wavelength.
6.2 MOLECULAR ABSORPTION SPECTROPHOTOMETRY

The instrument used for measurement of absorbance is known generally as a spectrophotometer. In
a spectrophotometer, radiant energy of a very narrow wavelength range is selected from a source and
passed through the sample solution, which is contained in a glass or quartz cell, called a cuvette. The
chemicals in the sample absorb some of the radiant energy, and the rest passes on through.
Spectrophotometry is a very fast and convenient method for quantitative analysis. The amount of ra-
diation absorbed (absorbance) at a specific wavelength is proportional to the concentration of the
light-absorbing chemical in the sample.
6.2.1 BASIC COMPONENTS OF SPECTROPHOTOMETER

The basic spectrophotometer consists of a light source, wavelength selector, sample holder or sam-
ple compartment, detector, and readout device, as shown in Figure 6.1.
6.2.1.1 Light Source

The light source provides the light directed at the sample. The selection of the source depends on
the region of the electromagnetic radiation needed for the analysis. There are considerable differ-
ences in technique and spectrum analysis between methods involving ultraviolet and visible
(UV/Vis) light and infrared (IR) light. UV/Vis spectrophotometry is used mostly for quantitative
89
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TABLE 6.1
Visible Spectrum and Complementary Colors
Wavelength (nm) Color Complementary Color
400–435 Violet Yellow-green
435–480 Blue Yellow
480–490 Green-blue Orange
490–500 Blue-green Red
500–560 Green Purple
560–580 Yellow-green Violet
580–595 Yellow Blue
595–610 Orange Green-blue
610–675 Red Blue-green
analysis; IR spectrophotometry is mostly a qualitative technique, although quantitative applications

can also be important.
The light sources for visible and UV radiation are presented in Table 6.2. The tungsten filament
lamp is the only common source for the visible region; it covers part of the UV region, but is gener-
ally not used below 320 to 330 nm. At shorter wavelengths, a deuterium lamp is used.
6.2.1.2 Wavelength Selector or Monochromator

The function of the monochromator is to select a beam of monochromatic (one-wavelength) radia-
tion. The essential parts of the monochromator follow:
1. The entrance slit controls the intensity of the light.

2. The lens or mirror causes light to travel as parallel rays.
3. The dispersion device selects light of different wavelengths. Dispersion devices include
diffraction gratings, prisms, and various optical filters.
a. A diffraction grating is a surface with a large number of parallel grooves. Light strik-
ing the grating is diffracted so that different wavelengths come off at different angles.
Rotating the grating, by turning the wavelength dial on the instrument, allows radia-
tion of the desired wavelength to be selected.
b. A prism disperses radiation by means of refraction. Radiation of different wave-
lengths is bent at different angles upon entering and emerging from the prism.
c. The simplest monochromators rely on optical filters. Instruments that use optical fil-
ters are inexpensive or portable and can be designed for specific analyses in the field.
Filters types include absorption filters, which have very wide bandwidths, absorb
Detector
Radiation Sample cell Measuring
Monochromator system
source compartment
Display
and
chart
recorder
FIGURE 6.1 Basic construction of a simple spectrophotometer.

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Molecular Spectrophotometry 91
TABLE 6.2
Ultraviolet and Visible Radiation Sources
Source Wavelength Range (nm) Intensity

Tungsten filament lamp 320–2500 Weak below 400 nm; strong above 750 nm
Tungsten halogen lamp (quartz envelope) 250–2500 —
Hydrogen discharge lamp 180–375 Weak at all wavelengths, but best in
200–325 region
Deuterium discharge lamp 180–400 Moderate
certain parts of the spectrum, and are made of colored glass. Interference filters reject
unwanted wavelengths and transmit a narrow bandwidth.
4. Lenses or mirrors are used to focus the light.
5. The exit slit controls the color (or wavelength) of the light that enters the sample
compartment.
6.2.1.3 Sample Holder or Compartment

A sample holder is a tight box where the sample is irradiated by the light emerging from the mono-
chromator. The sample, in the form of solution, is contained in an optically transparent cell, a cuvette,
with a known width and optical length. Cells are made of optical glass. Some inexpensive spec-
trophotometers use circular test-tube cuvettes.
Cells used in the visible region of light are made of optical-quality borosilicate glass. At about
320 nm, the glass begins to absorb most of the radiant energy. For lower wavelengths, it is necessary
to use more expensive cuvettes made of quartz or some other form of silica. Of course, these cells
can also be used above 320 nm.
Matched cuvettes are identical with respect to path length and reflective and refractive properties
in the area where the light beam passes. If the path length is different or if the wall of one cuvette re-
flects more or less light than another cuvette, then the absorbance measurement could be different,
rather than because of the concentration difference. Therefore, the cuvette must be placed in the in-
strument exactly the same way each time, as path length and refractive properties can change by ro-
tating the cuvette. A vertical line on the cuvette lined up with a similar line on the cuvette holder helps
to avoid the abovementioned source of error, as illustrated in Figure 6.2.
Protect cuvettes from scratches. When cleaning cuvettes, use soft cloths, and avoid the use of
abrasive cleaning agents. Avoid finger marks, lint, or dirt. When inserting a cuvette into the instru-
ment, grasp it at the top edge. Any liquid or fingerprints adhering to the outside wall of the cuvette
must be removed with a soft cloth or soft tissue prior to measurement.
Because of additional reflection from the air to glass surfaces, empty cuvettes transmit less radi-
ation than do cells filled with reference standards, blanks, or deionized water. Do not use an empty
cuvette to zero the instrument.
To avoid errors caused by removing a cuvette and then replacing it with another, spectropho-
tometers are available equipped with a fixed flow-through cell. The solution to be measured takes
about 30 to 60 sec to flow through the cell. The reading can be taken after the first few seconds, which
are needed to wash out the cell and fill it with the new sample.
6.2.1.4 Detector
A photosensitive detector picks up transmitted radiation through the solution. Detectors are phototubes,
which convert light energy into electrical energy. A typical phototube consists of a half-cylinder
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FIGURE 6.2 Lining up a cuvette for insertion into the cuvette holder.
Cathode
Beam of photons
(light)
Wire anode
Electrical contact
through prongs
FIGURE 6.3 Schematic diagram of a phototube showing the emission of an electron from the cathode to the
anode. A typical phototube consists of a half-cylinder cathode and a wire anode in a sealed evacuated glass tube.
A beam of photons passes through the sample and strikes the inner surface of the cathode and ejects electrons
from the cathode. The electrons migrate through the vacuum to the positive wire anode and produce a current.
cathode and a wire anode in a sealed, evacuated glass tube. Because the cathode emits electrons when
struck by photons, the phototube is called a photoemissive tube. The response of the phototube to dif-
ferent wavelengths depends on the composition of the cathode coating. A schematic diagram of a
phototube appears in Figure 6.3.
6.2.1.5 Readout Device

Radiation striking the detector generates electric current, which is increased via an amplifier and then
transmitted to a recorder or displayed on the spectrophotometer via a digital or scale readout. Digital
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Optical part
Source Monochromator Sample Detector
Electrical part
Amplifier
Readout
FIGURE 6.4 Block diagram showing components of a single-beam spectrophotometer. The optical and elec-
trical parts of the instrument meet at the detector, which converts radiant energy into electrical energy.
displays are now used except on the most inexpensive instruments. The readout can be either trans-
mittance or absorbance.
In a conventional spectrophotometer, the measured absorbance is used to calculate the concen-
tration of the measured sample component or to prepare a Beer’s law plot. Data manipulation re-
quires more time than the measurements. Modern spectrophotometers with built-in microprocessors
or microcomputers can perform rapid computations, store information for later use, and control many
meter operations. With such equipment, the operator inserts the cuvette into the instrument and uses
the keyboard to perform the measurements. Calibration plots are based on linear regression (see
Section 6.6.3) and may be graphically displayed.
6.3 SINGLE-BEAM AND DOUBLE-BEAM SPECTROPHOTOMETERS

Two general types of spectrophotometry instruments are available: single beam and double beam.
6.3.1 SINGLE-BEAM SPECTROPHOTOMETER

In single-beam instruments, all measurements are based on the varying intensity of a single beam of light.
All energy from the light source can be directed through the sample cell. Figure 6.4 presents a schematic
diagram of a single-beam optical system. The disadvantage of the single-beam instruments is that the
light intensity can change due to fluctuations occurring in the line voltage, power source, or light bulb.
Thus, an error could result in the sample reading. Single-beam lamp intensity drift has been controlled
by designing more stable light sources and lamp power supplies and prewarming of light sources.
6.3.2 DOUBLE-BEAM SPECTROPHOTOMETER

The double-beam instrument uses additional optics to divide the light from the lamp into a sample
beam (directed through the sample cell) and a reference beam (directed through the blank). A
schematic diagram of a typical double-beam instrument is shown in Figure 6.5. The light coming
from the monochromator is directed at one of two paths with a rotating half-mirror, called a chopper.
At one moment the light passes through the sample, while at the next moment it passes through the
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Computer
Analog–to–digital
converter
Mirror Reference Mirror
Signal
processor
Detector
Source Monochromator Sample Half-mirror

Chopper
(rotating
mirror)
FIGURE 6.5 Schematic diagram of a double-beam spectrophotometer. The light coming through the mono-
chromator is directed along either one of two paths with the use of a “chopper” or rotating half-mirror. At one
moment the light passes through the sample, while at the next moment it passes through the blank. Both beams
are joined again with a second rotating half-mirror prior to entering the detector.
blank. Both beams are joined again with a second rotating half-mirror prior to entering the detector.
The detector sees alternating light intensities and automatically compensates for fluctuations, usually
by automatically widening or narrowing the entrance slit to the monochromator. If the beam becomes
less intense, the slit is opened; if the beam becomes more intense, the slit is narrowed. Thus, the sig-
nal relayed to the readout device is free of effects of intensity fluctuations from the source.
6.4 TYPES OF SPECTROPHOTOMETERS

Spectrophotometric instruments vary greatly in price, performance, and sophistication.
6.4.1 VISIBLE SPECTROPHOTOMETER

These instruments have inexpensive optical glass components and operate in the wavelength range of
325 nm to 900–1000 nm. Older instruments, such as the Spectronic 20, select wavelengths mechani-
cally through a wavelength knob, whereas modern, digital-readout instruments offer electronic wave-
length selection via a keyboard. Older instruments rely on blue- and red-sensitive phototubes.
6.4.2 ULTRAVIOLET/VISIBLE (UV/VIS) SPECTROPHOTOMETER

The UV/Vis spectrophotometer is designed for measurements in the ultraviolet and visible regions.
Such instruments measure absorption in the 200- to 1000-nm region. For measurements below the
320-nm region, the spectrophotometer must be equipped with an ultraviolet source of radiation. The
most common source of radiation in the visible region is the tungsten filament lamp, and in the UV
region, the deuterium discharge lamp. In some spectrophotometers, the tungsten halogen lamp can
be used for measurements as low as 250 or 220 nm. Light sources for UV/Vis radiation are listed in
Table 6.2.
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6.4.3 SPECTROPHOTOMETERS WITH A BUILT-IN MICROPROCESSOR

OR MICROCOMPUTER
Modern spectrophotometers with a built-in microprocessor or microcomputer can perform rapid data
processing and control many instrument operations. In such instruments, the operator inserts one or
more cuvettes into the instrument and uses the keyboard to punch in the necessary operating in-
structions. Calibration plots are based on linear regression calculations and may be graphically dis-
played. Linear regression is discussed in Section 6.6.3.
6.4.4 DIFFERENCES BETWEEN UV/VIS AND IR SPECTROPHOTOMETRIC METHODS

Methods involving ultraviolet and visible (UV/Vis) light and infrared (IR) light are quite different:
1. UV/Vis spectrophotometry is generally considered a quantitative analysis technique,

while IR is considered a qualitative technique. However, both techniques may be utilized
in a given analysis.
2. In the UV/Vis technique, absorption spectra are recorded, while transmittance spectra are
used in the IR technique.
3. UV/Vis spectra are created from electronic transitions, while IR spectra arise from mo-
lecular vibrational transitions. Consequently, the IR technique provides more specific data
about molecular structure.
4. UV/Vis and IR instruments are different in design, cuvette materials, and sample prepara-
tion techniques.
6.4.5 INFRARED (IR) SPECTROPHOTOMETER

The IR spectrophotometer has the same basic components as UV/Vis instruments, but the radiation
source used in the optical system, sample cells, and detectors are different.
6.4.5.1 Light Source

For visible light, the light source is a tungsten-filament lamp; for UV light, a hydrogen discharge
lamp is the most common. For infrared light, a heat source is necessary. The two most important in-
frared sources are glowing silicon carbide rods (Globars) and rods made of the rare earth oxides zir-
conium and yttrium oxides (Nernst glowers). Incandescent nichrome wires are also common.
6.4.5.2 Monochromator System

The monochromator systems in the IR and UV/Vis spectrophotometers are the same. The only dis-
persing device used for wavelength selection in the infrared is the diffraction grating.
6.4.5.3 Sample Cells

When using visible light, the cuvette may be made of any clear, colorless, transparent material, in-
cluding glass and plastic. Cuvettes used for measurements in the UV region must be made of quartz
glass. Both glass and quartz absorb infrared radiation; therefore, the monochromator optics and cells
must be made from ionic materials. Large, polished sodium chloride (NaCl) crystals are most often
used. Cells made of lithium fluoride (LiF) or calcium fluoride (CaF2) provide better resolution at
lower wavelengths, and cells made of potassium bromide (KBr) or cesium iodide (CsI) are more use-
ful at higher wavelengths. The salt crystals are placed in some type of fixture, such as a demountable
cell. A small amount of liquid sample, introduced through a sample port with a syringe, is held within
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a gasketed space inside and in the path of the light beam when placed in the instrument. Of course,
because salts are highly water soluble, water cannot be used as a solvent for the sample. Usually sol-
vents such as carbon tetrachloride (CCl4) or methylene chloride (CH2Cl2) are used because their spec-
tra show very little or no absorption in the IR region.
6.4.5.4 Detector
Infrared radiation can be measured by detecting the temperature change of a material in the infrared
beam; this type of detector is known as a thermal detector. Because the radiant power of infrared ra-
diation is so weak, the response of most thermal detectors is quite low. A preamplifier is usually nec-
essary to obtain a good signal-to-noise ratio in the amplifier. Another problem is heat radiated from
objects in the room. To minimize this source of error, the detector must be housed in a vacuum or
shielded from direct exposure to heat.
6.4.5.6 Readout
In ultraviolet and visible spectra, absorbance and transmittance are plotted against wavelengths. In
infrared spectra, using wavenumbers is preferred over wavelengths. The wavenumber is the recipro-
cal of wavelength expressed in centimeters, and therefore has a unit of cm–1. See Figure 6.6 for wave-
length and wavenumber conversion.
The IR region of the spectrum is usually considered to start near the red end of the visible spec-
trum at the point where the eye no longer responds to dispersed radiation (“infra” means below the
red). The fundamental IR region extends from 3600 cm–1 (wavenumber) or 2.8 µm (wavelength). The
analytically useful IR region extends from 3600 cm–1 to somewhere around 300 cm–1 or 33 µm.
Infrared spectrophotometers are generally double-beam instruments. The sample cell and refer-
ence cell (solvent) are exposed to equivalent beams from the same infrared source. A rotating half-
circle mirror is used to direct an equivalent beam alternately through the two cells many times a sec-
ond. Thus, any condition that affects the sample beam equally affects the reference beam, so that the
condition is canceled out in the readout. (Double-beam instruments are discussed in Section 6.3.2
and the schematic diagram of the operation appears in Figure 6.5.)
6.4.5.7 Samples
Samples can be liquids, solids, or gases. They can be organic or inorganic, although inorganic mate-
rials sometimes do not give very definitive spectra. The only molecules transparent to IR radiation
under ordinary conditions are monatomic and nonpolar molecules, such as Ne, He, O2, N2, and H2.
Liquid samples may be analyzed without dilution or being dissolved in a solvent. Running a liq-
uid sample without a solvent (pure or “neat” sample) is desirable.
Two methods are available for analyzing solids without dissolving them. In the first method, the
potassium bromide (KBr) pellet technique, a small portion of the dry solid sample is mixed with
potassium bromide. A small amount of this mixture is then transferred to a “pellet die,” in which the
mixture is pressed into a potassium chloride pellet. The pellet is a transparent half-inch disk that can
Wavenumber, cm-1
10000 5000 3000 1800 1400 1200 1000 900 800 700 650 600 550 500
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Wavelength, µm
FIGURE 6.6 Conversion of wavelength and wavenumber.

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be placed directly in the radiation path. In the other method, known as the mull method, the dry solid
sample is mixed with mineral oil so that the substance becomes “toothpaste-like.” This mixture is
then placed between two salt crystals and the spectrum recorded.
6.5 SUMMARY OF MOLECULAR SPECTROPHOTOMETRY
Region Ultraviolet (UV) Visible (Vis) Infrared (IR)
Wavelength 180 to 400 nm 400 to 750 nm 750 to 15,000 nm

Light source Hydrogen discharge tube Tungsten-filament lamp Globar, Nernst glower,
incandescent nichrome wire
Cuvette material Quartz Glass or clear plastic Inorganic salt crystal
Detector Phototube Phototube Thermal detector
6.6 SPECTROPHOTOMETER CALIBRATION

Calibrations are performed at the beginning of the analysis to ensure that the instrument is working
properly. This initial calibration is determined for each parameter tested, based on instrument re-
sponse for different calibration standards against the calibration blank. The optimum concentration
range and the number of these standards are determined by the analytical method. The concentration
of calibration standards should be bracketed in the optimum range. The concentration of standards
and the measured response (absorbance, transmittance, etc.) of the instruments should plot on the
calibration curve and be approved by calculating the corresponding correlation coefficient.
Computerized, modern instruments display the curve and the value of the correlation coefficient. Its
value should be greater than 0.9998, which serves as a basis for acceptance or rejection of the cali-
bration curve. In UV/Vis spectrophotometers, the initial calibration is based on a 4- to -6-point stan-
dard curve in the optimum linear range as stated in each particular parameter.
After the calibration curve is established, once for each analytical batch (samples that are ana-
lyzed together with the same method and the same lot of reagents) or at a 5% frequency, the curve
should be approved with a continuing calibration. The latter includes the analysis of the continuing
calibration standard (CCS) and calibration verification standard (CVS) and must be analyzed be-
fore samples are measured. The CCS value is a midpoint initial calibration standard. Deviation from
the original value should be within ±5%. The CVS should be a certified standard or independently
prepared from a source other than the calibration standards. Its analyzed value is accepted within
±10% deviation from the 100% recovery.
Sample pretreatments (digestion, distillation, extraction, filtration, etc.) should be verified, and
the effects of sample preparations should be monitored. To support these measures, a blank (prepa-
ration blank) and one standard (laboratory control standard, LCS) should be prepared and analyzed
together with the samples. The preparation blank or “prep blank” is analyte-free water treated in the
same way as the samples. The LCS is a sample taken from the CVS, except that it is carried through
the preparation. Accepted values are within ±15% deviation from the 100% recovery.
6.6.1 FREQUENCY OF CALIBRATION CURVE PREPARATION

Frequency depends on the instrumentation. For the UV/Vis spectrophotometer, use the available cal-
ibration curve until the correct calibration is approved, which is performed every 6 months or on the
failure of any continuing calibration standard. Daily calibration is made by zeroing the instrument
with a calibration blank and measurement at one continuing calibration standard (CCS) with a ±5%
L1572_C06 5/23/02 1:24 PM Page 98
recovery and with the ±10% recovery of a calibration verification standard (CVS). Once per analyt-
ical batch or with 5% frequency, this check should be repeated. If the CCS and CVS fail, the cali-
bration criteria of the analysis must be stopped and a new initial calibration performed. Samples
measured before the failed standards must be analyzed again.
6.6.2 GENERAL RULES IN THE PREPARATION OF CALIBRATION CURVES

Calibration curves are prepared by taking standards of known concentrations. For the preparation of
calibration curves, ordinary rectangular-coordinate paper is generally satisfactory. For some graphs
(e.g., measurement of millivolt response by using a pH meter with ion-selective electrodes), semi-
logarithmic paper is preferable. Plot the independent and dependent variables on the abscissa and or-
dinate in a manner that can be comprehended easily, and cover as much of the graph paper as possi-
ble. Choose the scales so that the slope of the curve approaches unity as nearly as possible and choose
the variables so that the plot will be close to a straight line. Graph legends should provide complete
information about the conditions under which the data were obtained, including the parameter de-
termined, method and reference, volume of the standards, wavelength used, time between addition
of reagents and the reading, data obtained from the linear regression calculation, date of preparation,
and name and signature of the preparer. A typical calibration curve appears in Figure 6.7.
6.6.3 LINEAR REGRESSION CALCULATION

When a calibration curve is prepared, the sample concentration is obtained by measuring the in-
strument response under the same conditions used for the standards; sample concentration is read
on the horizontal axis of the plot. Although unknown concentrations can be read directly from the
graphical plot, better accuracy is possible by using the linear regression calculation, also called the
least squares calculation. In this calculation, of the possible straight lines that can be drawn through
or near the data points, the one chosen minimizes the sum of the squared deviations. The deviation
for each point is the difference between the actual data points with the same x-axis value that lies
exactly on the straight line. It gives information about the best straight line through the points en-
tered, including the correlation coefficient, intercept, slope, and the predicted x and y values.
The correlation coefficient is the correlation between the x and y values in a set of data points.
The closer the coefficient is to one, the stronger the direct or positive linear relationship (an increase
in one variable is related to an increase in the other). The closer the coefficient is to minus one, the
stronger the indirect or negative linear relationship (an increase in one variable is related to a decrease
in the other). A value of greater than 0.9998 is accepted.
Intercept b tells whether there is a significant blank measurement even when the concentration
of the blank is zero. The intercept value is the y intercept of the best straight line through the points.
The calculated value of the slope m is the slope of the best straight line. The formulas for calculating
these values follow:
m = nExy – ExEy/nE2 – (Ey)2 (6.1)
b = nEy2 – EyExy/nEy2 – (Ey)2 (6.2)
where
m = slope.
b = intercept.
E = sum.
x = concentration.
y = absorbance (or other response).
L1572_C06 5/23/02 1:24 PM Page 99
Spectrophotometer's model: Date : May 23, 1993

Sequoia Turner 690 Prepared by :
SULFATE (SO2–
4)
(Turbidimetric method)
Standards Absorbances Wavelength : 420 nm

0.50 10 ppm 0.12
20 ppm 0.26
30 ppm 0.39
40 ppm 0.52
Corr. coeff. : 0.9998
0.40
Note : Above 40 ppm accuracy Sample size : 100 ml
decreases and BaSO4 suspension Read : at 5 +- 0.5 min
loses stability BaCl2 specification:
dihydrate, Fisher,
0.30 Batch No. : 02990
Absorbance
0.20
0.10
10 20 30 40 ppm
FIGURE 6.7 Typical calibration curve.
When the absorbance is known, the slope and intercept values of the concentration of the sam-
ple can be calculated according to the formula,
x = my + b (6.3)
For example, in a spectrophotometric analysis, the initial calibration provides the following data:
Number of the standards (n) = 6

Concentration of the standards (x) = 0.2, 0.4, 0.5, 0.6, 0.8, and 1.0 ppm
Measured absorbances (y) = 0.206, 0.392, 0.503, 0.598, 0.789, and 0.992
Calculated correlation coefficient = 0.99985
Using the linear regression calculation, predict the slope and intercept values for the above data
with the formulas (6.1), (6.2), and (6.3):
x y y2 xy
0.2 0.206 0.042 0.041
0.4 0.392 0.154 0.157
0.5 0.503 0.253 0.252
0.6 0.598 0.358 0.359
0.8 0.789 0.623 0.631
1.0 0.991 0.982 0.991
E= 3.5 3.479 2.412 2.431
m = (6 × 2.431) – (3.5 × 3.479)/(6 × 2.412) – (3.4792) = (14.586 – 12.177)/(14.472 – 12.103) = (2.409/2.369) = 1.107
b = (2.412 × 3.5) – (3.479 × 2.431)/(6 × 2.431) – (3.4792) = (8.442 – 8.457)/(14.472 – 12.103) = – (0.015/2.369) = –0.006
L1572_C06 5/23/02 1:24 PM Page 100
Absorbance for a sample of unknown concentration measured as 0.246. By using formula 6.3, the
sample concentration is:
x = 1.017 × 0.246 + (−0.006) = 0.244 ppm
6.7 PERFORMANCE CHECK OF UV/VIS AND IR SPECTROPHOTOMETER

Spectrophotometer designs and models vary. The manufacturer’s manual and the laboratory’s stan-
dard operating procedures (SOPs) should be consulted for correct operation and maintenance. In ad-
dition to calibration, performance of instruments for accuracy must be checked periodically.
6.7.1 UV/VIS SPECTROPHOTOMETER

For UV/Vis spectrophotometers, wavelength calibrations and linearity checks are recommended.
Wavelength accuracy can be checked with a commercially available didymium calibration filter, or with
the very simple cobalt chloride test. In the latter test, measure the absorbance of a cobalt chloride solu-
tion (22 g of CoCl2 dissolved and diluted to 1 liter with 1% HCl solution) on 500-, 505-, 510-, 515-, and
520-nm wavelengths. The wavelength calibration check is satisfactory if maximum absorbance or min-
imum transmittance occurs between the 505- and 515-nm wavelengths. Perform a linearity check by
measuring the absorbance at 510 nm of the cobalt chloride solution used for the wavelength calibration,
and at the same wavelength the absorbance of the 1:1 dilution of this solution. The absorbance of the
1:1 diluted solution should be half of the original reading. Documentation of the wavelength and lin-
earity checks is illustrated in Figures 6.8. and 6.9, respectively.
FIGURE 6.8 Documentation of spectrophotometer wavelength calibration check. nm = nanometer, unit of the
wavelength. The calibration check is satisfied when maximum absorbance (or minimum transmittance) occurs
between 505 and 515 nm wavelengths.
FIGURE 6.9 Documentation of spectrophotometer linearity check. The absorbance of the 1:1 diluted cobalt
solution should be half reading produced by the stock cobalt solution (22 g CoCl2 in 1 L 1% HCl solution).
L1572_C06 5/23/02 1:24 PM Page 101
6.7.2 IR SPECTROPHOTOMETER
Satisfactory operation of an IR spectrophotometer is determined with commercially available 0.05-
mm-thick polystyrene film. Record the spectrum of this film and compare it with the reading supplied
by the manufacturer. If the test spectrum is not within the indicated tolerance, adjustment is neces-
sary, probably by a service representative. See Figure 6.10.
6.8 MAINTENANCE OF THE UV/VIS AND IR SPECTROPHOTOMETERS

Proper care and maintenance of the instruments are the basic requirements for accurate and sufficient
laboratory results.
6.8.1 UV/VIS SPECTROPHOTOMETER

Recommended daily, weekly, and quarterly maintenance chores for a UV/Vis spectrophotometer are
summarized:
1. On a daily basis, keep the sample compartment and cuvettes sparkling clean.
2. Check lamp alignment on a weekly basis.
3. Under the service contract, an instrumentation specialist must clean the windows.
6.8.2 IR SPECTROPHOTOMETER
Recommended daily, weekly, and quarterly maintenance chores for a UV/Vis spectrophotometer are
summarized below.
1. Clean the sample cell and check for gas leakage every day.
2. Clean windows on a monthly basis.
3. Change the desiccant every quarter.
Infrared Spectra of Polystyrene

100
80
60
Transmittance (%)
3
A
40 5
B 7
20
2 4 6 9
1 8
4000 3300 3000 2300 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm–1)
FIGURE 6.10 Performance check of infrared (IR) spectrophotometer.

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L1572_C07 5/23/02 1:26 PM Page 103
Atomic Absorption
7 Spectrometry
7.1 INTRODUCTION
7.1.1 ATOMIC SPECTROMETRY (AS)
As discussed previously, AS is a class of elemental analysis techniques that use the interaction of
electromagnetic radiation with atoms or ions to detect the presence of elements of interest.
7.1.2 ATOMIC ABSORPTION (AA)

Atomic absorption occurs when a ground-state atom absorbs energy in the form of light of a specific
wavelength and is elevated to an excited state. The amount of light energy absorbed at this wave-
length increases as the number of atoms of the selected element in the light path increases. The rela-
tionship between the amount of light absorbed and the concentration of analyte present in known
standards can be used to determine unknown concentrations by measuring the amount of light ab-
sorbed. Instrument readouts can be calibrated to directly display concentrations.
7.1.3 ATOMIC ABSORPTION SPECTROMETRY (AAS)

Atomic absorption spectrometry is an element analysis technique that uses absorption of electromag-
netic radiation to detect the presence of the elements of interest. Molecular spectrophotometry and
working techniques were discussed in Chapter 6; this chapter focuses on analytical methods using
atomic spectra. This technique has been applied to the determination of numerous elements and is a
major tool in studies involving trace metals in the environment and in biological samples. It is also fre-
quently useful in cases where the metal is at a fairly high concentration level in the sample but only a
small sample is available for analysis, which sometimes occurs with metalloproteins, for example. The
first report of an important biological role for nickel was based on a determination via AA that the ure-
ase enzyme, at least in certain organisms, contains two nickel ions per protein molecule.
Light absorption is measured and related to element concentration in both AAS and molecular
spectrophotometry (see Chapter 6). The major differences lie in instrument design, especially with
respect to the light source, sample cell, and placement of the monochromator. As outlined in previ-
ous chapters, the absorption of light by individual, nonbonded atoms must be considered separately
from molecular absorption. In atoms, all energy transitions are electronic; therefore, only individual,
discrete, electronic transitions are possible. Consequently, atomic spectra are made up of lines, which
are much sharper than the bands observed in molecular spectroscopy. Each discrete energy increase
is due to the absorption of the wavelength corresponding to an energy transition; therefore, only those
wavelengths are absorbed, and only those wavelengths show up in the atomic spectrum, or line spec-
trum. Atomic absorption spectra are produced when the free atoms absorb radiant energy at charac-
teristic wavelengths. To produce an atomic spectrum, a compound must first absorb enough energy
to vaporize it to a molecular gas and dissociate the molecules into free atoms. Because the amount of
103
L1572_C07 5/23/02 1:26 PM Page 104
light absorbed by a sample is proportional to the concentration of the absorbing species, light ab-
sorption can be used in quantitative analytical chemistry.
Metals in solution can be readily determined by AAS. The method is simple, rapid, and applica-
ble to a large number of metals in different samples. While drinking water that is free of particulate
matter can be analyzed directly, samples containing suspended material, sludge, sediment, and other
solids are analyzed after proper pretreatment. Sample preparations are discussed in Chapter 15.
7.1.3.1 Atomic Absorption Measurement

The light of a wavelength, which is characteristic of the element of interest, is beamed through an
atomic vapor. Some of this light is then absorbed by the atoms of the element. The amount of light
that is absorbed by these atoms is then measured and used to determine the concentration of that el-
ement in the sample. The use of special light sources and careful selection of wavelengths allow the
specific quantitative determination of individual elements in the presence of others. The atom cloud
required for atomic absorption measurements is produced by supplying enough thermal energy to the
sample to dissociate the chemical compounds into free atoms. Aspirating a solution of the sample
into a flame aligned in the light beam serves this purpose. Under the proper flame conditions, most
of the atoms will remain in the ground-state form and are capable of absorbing light at the analytical
wavelength from a source lamp. The light is then directed onto the detector where the reduced in-
tensity is measured.
7.2 STEPS IN THE ATOMIC ABSORPTION PROCESS

The solvent is evaporated or burned, and the sample compounds are thermally decomposed and con-
verted into a gas of the individual atoms present. The atoms of this element in the flame absorb light
only from the hollow-cathode source that emits the characteristic wavelength of the single element
being determined. Some of the light is absorbed and the rest passes through. The amount of light ab-
sorbed depends on the number of atoms in the light path. The selected spectral line from the light
beam is isolated by a monochromator. The wavelength of light selected by the monochromator is di-
rected onto the detector. The detector is a photomultiplier tube that produces an electrical current de-
pendent on the light intensity. The electrical current from the photomultiplier is then amplified and
processed by the instrument electronics to produce a signal that is a measure of the light attenuation
occurring in the sample cell. This signal can be further processed to produce an instrument readout
directly in concentration units. Steps of the above process are described in the following sections.
7.2.1 NEBULIZATION
Aspirate the sample into the burner chamber. The sample becomes an aerosol and mixes with the fuel
and oxidant gases. In this step the metals are still in solution in the fine aerosol.
7.2.2 EVAPORATION OR DESOLVATION

The aerosol droplets move into the heat of the flame, where the solvent is evaporated and solid par-
ticles of the sample remain.
7.2.3 LIQUEFACTION AND VAPORIZATION

Heat is applied and the solid particles are liquefied. With additional heat, the particles will vaporize.
At this point, the metal of interest (analyte) still contains anions to form molecules.
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Atomic Absorption Spectrometry 105
7.2.4 ATOMIZATION
By applying more heat, the molecules are broken down and individual atoms form.
7.2.5 EXCITATION AND IONIZATION

The ground-state atoms formed during the atomization step will excite and determine the amount of
light absorbed. Concentration is determined by comparing the absorbance of the sample to standards
with known concentrations.
7.3 ATOMIC ABSORPTION SPECTROPHOTOMETER COMPONENTS

7.3.1 LIGHT SOURCE
As indicated previously, an atom absorbs light at discrete wavelengths. To measure this narrow light
absorption with maximum sensitivity, it is necessary to use a light source that emits specific wave-
lengths which can be absorbed by the atom. In other words, the light emitted from the lamp should
be exactly the light required for the particular analysis. To satisfy this criterion, the atoms of the ele-
ment tested are present in the lamp. When the lamp is on, these atoms are supplied with energy that
causes them to enter into excited states. When the promoted atoms return to their ground state, the
light energy will be emitted at the wavelength characteristic to the metal. Thus, each metal analyzed
requires a separate source lamp. The most common light sources used in atomic absorption are the
hollow cathode lamp and the electrodeless discharge lamp.
The hollow cathode lamp (HCL) is an evacuated glass tube filled with either neon or argon gas.
The HCL is illustrated in Figure 7.1. The cathode (− charged electrode), which is made of the metal
to be determined, and the anode (+ charged electrode) are sealed in the tube. A window, transparent
to the emitted radiation, is at the end of the tube. When the lamp is on, an electrical potential is applied
between the anode and cathode, and the gas atoms are ionized. The actively charged gas ions collide
with the cathode and liberate metal atoms. These atoms are excited by the energy liberated through the
collision. By returning to the ground state, the atoms emit light energy as described above. HCLs have
a limited lifetime. Because of the rapid vaporization of the cathode for volatile metals, such as arsenic
(As), selenium (Se), and cadmium (Cd), the lifetime of these lamps is especially short.
It is possible to construct a cathode from several metals. This kind of lamp is called a multi-
element lamp. The intensity of emission for an element in a multielement lamp is not as great as that
observed for the element in a single-element lamp. Thus, special consideration is necessary before using
multielement lamps in applications where high precision and low detection limits are necessary.
Anode Window
Ar
Cathode Fill gas
FIGURE 7.1 Hollow cathode lamp.

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RF Coil
Quartz
Window
Lamp
Ceramic
Holder
FIGURE 7.2 Electrodeless discharge lamp.
In some applications — primarily in the determination of volatile elements — the resistivity of

the HCL is not satisfactory. The analytical performance of these elements by AA can be improved
dramatically by using electrodeless discharge lamps (EDLs). EDLs offer the analytical advantages
of better precision and lower detection limits. In addition to providing superior performance, the use-
ful lifetime of an EDL is much longer than that of a HCL for the same element. EDL design is illus-
trated in Figure 7.2. A small amount of the metal or its salt is sealed inside a quartz bulb. The bulb is
placed inside a ceramic holder on which the antenna from a radio frequency (RF) generator is coiled.
When an RF field of sufficient power is applied, the coupled energy will vaporize and excite the
atoms inside the bulb, causing them to emit their characteristic spectrum. An accessory power sup-
ply is required to operate an EDL.
7.3.2 FLAMES
In order for the atomic absorption process to occur, individual atoms must be produced from the sam-
ple, which starts out as a solution of ions. The function of the flame is to evaporate the solvent, de-
compose and dissociate molecules, and provide ground-state atoms for absorption of the emitted ra-
diation. All flames require both a fuel and an oxidant.
The two flames used for AA are air–acetylene and nitrous oxide (N2O)–acetylene. In the case of
air–acetylene flames, acetylene is the fuel and air is the oxidant. The temperature is 2130 to 2400°C.
In the nitrous oxide–acetylene flame, acetylene is the fuel but nitrous oxide is used as an oxidant. The
temperature of this flame is 2600 to 2800°C.
While the air–acetylene flame is satisfactory for the majority of elements determined by atomic
absorption spectrophotometry, the hotter nitrous oxide–acetylene flame is required for many refrac-
tory-forming elements. The recommended flame used for any given element is available in reference
books or in the application manual issued by the manufacturer of the instrument.
7.3.3 NEBULIZER AND BURNER

Typically, the nebulizer (often called atomizer) and burner comprise a single unit.
7.3.3.1 Nebulizer
The purpose of the nebulizer is to suck up the sample and spray it into the flame at a constant and re-
producible rate. In order to provide for the most efficient nebulization for variable sample solution
systems, the nebulizer should be adjustable. The most common material of the nebulizer is stainless
steel, but this material corrodes in contact with highly acidic samples. A nebulizer made of corrosion-
resistant materials, such as plastic or platinum–rhodium alloy, is preferable.
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7.3.3.2 Burner
Two basic types of burner are used in atomic absorption spectrophotometers: “total consumption
burner” and “premix burner.”
• In the total consumption burner, the channels of the fuel gas, oxidizing gas, and sample
meet in a single opening at the base of the flame. The resulting flame is turbulent and non-
homogeneous. This type of burner is used in flame photometry.
• The premix burner produces a quieter flame that is less turbulent and homogenous; there-
fore, it is preferable in atomic absorption.
The sample is nebulized and mixed with the fuel and oxidant before introducing it to the flame.
Only the finest droplets of the nebulized sample enter the flame; the larger droplets are caught and
rejected through a drain. The drain uses a liquid trap to prevent combustion gases from escaping
through the drain line.
To deflect larger droplets and remove them from the burner through the drain, an impact device
is placed in the front of the nebulizer. The impact device can be a flow spoiler or a glass or ceramic
spoiler. For routine work, a chemically inert flow spoiler is preferred; glass beads may be used in
cases where additional sensitivity is needed. Components of an atomic absorption burner system are
shown in Figure 7.3.
Burner heads are constructed of titanium to provide extreme resistance to heat and corrosion. For
various types of flames, diverse burner-head geometries are required. For the air–acetylene flame, a
10-cm, single-slit burner head is used, and, for the nitrous oxide–acetylene flame, a 5-cm slit burner
head is recommended.
7.3.4 OPTICS AND MONOCHROMATOR SYSTEM

The function of the monochromator is to isolate a single line of the analyte’s spectrum. Light from the
source must be focused on the sample cell and directed to the monochromator at the entrance slit and
then directed to the grating where dispersion takes place. The grating consists of a reflective surface
with many fine, parallel lines very close together. Reflection from this surface generates an interference
known as diffraction, in which different wavelengths of light diverge from the grating at different
Flow Spoiler
Mixing Chamber
With Burner Head
Nebulizer
Impact Bead
End Cap
FIGURE 7.3 Premix burner system.

L1572_C07 5/23/02 1:26 PM Page 108
Exit slit
Photomultiplier
Grating
Entrance slit
FIGURE 7.4 A monochromator.
Light chopper Flame
Detector Readout
Source Monochromator
Fuel Air
Sample
FIGURE 7.5 Basic AA instrument.
angles. By adjusting the angles of the grating, a selected emission light from the source is allowed to
pass through the exit slit and focuses on the detector. Curved mirrors within the monochromator com-
prise the focusing control of the source lamp. A typical monochromator design is shown in Figure 7.4.
The size of the entrance and exit slits should be the same. The size of the slit is variable and ad-
justed for each element analyzed, according to recommendations by the instrument manufacturer and
pertinent reference materials.
7.3.5 DETECTOR
The detector measures the light intensity and transfers it to the readout system. The detector is a mul-
tiplier phototube, or photomultiplier (PM) tube.
7.3.6 READOUT SYSTEM

As with molecular spectrophotometry, the readout of the absorbance and transmittance data consists
of a meter, recorder, or both. Modern atomic absorption instruments include microcomputer-based
electronics. Figure 7.5 shows the basic components of an atomic absorption spectrophotometer.
L1572_C07 5/23/02 1:26 PM Page 109
7.3.7 AUTOMATIC SAMPLERS

Automatic samplers offer labor and time savings and thus speed up the analytical process.
7.3.8 AUTOMATED MULTIELEMENT AA INSTRUMENTS

These instruments set up parameters to preprogrammed values and make it possible to analyze mul-
tiple elements in a tray full of samples without operator intervention.
7.3.9 MICROCOMPUTER-BASED ELECTRONICS

Most modern instruments include microcomputer-based electronics. AA instruments are provided
with calculation and calibration abilities. Computers can be connected to the instrument output ports
to receive, manipulate, and store data and to print reports of calculations.
7.4 SINGLE- AND DOUBLE-BEAM INSTRUMENTS

The differences between single- and double-beam spectrophotometers were discussed in Chapter 6. In
the AA technique, the double-beam optical design is generally preferable. Double-beam technology,
which automatically compensates for source and common electronics drift, allows these instruments
to begin the analysis immediately after the installation of the lamp, with little or no warm-up. This not
only reduces analysis time but also prolongs lamp life, as lamp warm-up time is eliminated. Optimized
double-beam instruments offer excellent performance, high-speed automation benefits, and opera-
tional simplicity. Schematic outlines of the single- and double-beam spectrophotometers are shown in
Figures 6.4 and 6.5, respectively.
7.5 ATOMIC ABSORPTION MEASUREMENT TERMS

7.5.1 CALIBRATION
Calibrations are performed at the beginning of the analysis to ensure that the instrument is working
properly. Calibrations must be performed according to the analytical methods to be used. Initial cal-
ibration is determined for each parameter tested and based on the instrument responses for different
concentrations of standards, known as calibration standards. The number and optimum concentra-
tion range of the calibration standards used for each particular method are provided by the approved
methodology. A minimum of a blank and three standards must be utilized for calibration. Calibration
varies according to the type and model of the equipment. Detailed operation and calibration proce-
dures for each instrument are available in the laboratory’s standard operation procedures (SOPs) and
the manufacturer’s instructions. The instrument response should be linear with the concentration of
the introduced standards and plot on a calibration curve, or the instrument software should automat-
ically prepare a curve. Details of calibration curve preparation and the calibration process are pro-
vided in Chapter 6.
Calibration accuracy during each analytical run should be ensured via continuing calibration.
The continuing calibration standard represents the midpoint initial calibration standard. To confirm
the calibration curve and to verify the accuracy of the standards and the calibration, run a standard
prepared from another source as the calibration standards. Prepare standard solutions of known metal
concentrations in water with a matrix similar to the sample.
For samples containing high and variable concentrations of matrix materials, make the major
ions in the sample and the standards similar. If the sample matrix is complex and components can-
not be matched accurately with standards, use the method of standard addition (see Section 7.7.1). If
L1572_C07 5/23/02 1:26 PM Page 110
digestion or another method is used for sample preparation (see Chapter 15), carry standards through
the same procedure used for samples.
The range of concentrations over which the calibration curves for an analyte are linear is called
the linear dynamic range. The highest concentration for an analyte that will result in a linear ab-
sorption signal response is the maximum linear concentration.
7.5.2 CONCENTRATION
When the absorbance of standard solutions containing known concentrations of analyte are measured
and the absorbance data plotted against the concentration, a calibration relationship is established.
(See calibration details in Section 6.6.) Directly proportional behavior between absorbance and con-
centration (Beer’s law, see Section 5.5) is observed in atomic absorption.
After such calibration, the absorbance of solutions of unknown concentrations may be measured
and the concentration determined from the calibration curve. In modern instrumentation, the cali-
bration can be made within the instrument to provide a direct readout of unknown concentrations.
Built-in microcomputers make accurate calibration possible, even in the nonlinear region.
7.5.3 SENSITIVITY
Sensitivity or “characteristic concentration” is a convention for defining the magnitude of the ab-
sorbance signal that will be produced by a given concentration of analyte. For flame absorption, this
term is expressed in milligrams per liter (mg/l) required to produce a 1% absorption (0.0044 ab-
sorbance) signal:
Sensitivity (mg/l) = concentration of standard × 0.0044/measured absorbance (7.1)
7.5.4 DETECTION LIMIT (DL)

The DL is the smallest measurable concentration at which the analyte can be detected with a specific
degree of certainty. The detection limit may be defined as the concentration that will give an ab-
sorbance signal of two (sometimes three) times the magnitude of the baseline noise. The baseline
noise can be statistically quantitated by making ten or more replicate measurements of the baseline
absorbance signal observed for an analytical blank (reagent blank) and determining the standard de-
viation of the measurements. Therefore, the DL is the concentration that will produce an absorbance
signal twice (or three times) the standard deviation of the blank.
Details of the method detection limit, instrument detection limit, and practical detection limit
(PDL) are provided in Section 13.8.
7.5.5 OPTIMUM CONCENTRATION RANGES

The optimum concentration range usually starts from the concentration of several times the sensitiv-
ity and extends to the concentration at which the calibration curve starts to flatten. To achieve best
results, use concentrations of samples and standards within the optimum concentration ranges.
Sensitivity, detection limits, and optimum ranges vary according to complexity of the matrix, element
determined, instrument models, and technique. Table 7.1 shows detection limits obtainable by direct
aspiration and furnace techniques for 34 metals.
The concentration range may be extended downward by scale expansion, and extended upward
by dilution, using a less sensitive wavelength, rotating the burner head, or utilizing a microprocessor
to linearize the calibration curve at high concentrations. Detection limits by direct aspiration may
also be extended through concentration of the sample. Lower concentrations may also be detected by
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TABLE 7.1
Atomic Absorption Concentration Rangesa
Flame AA Graphite AA
Detection Optimum Detection Optimum
Limit Concentration Limit Concentration
Metal (mg/l) Range (mg/l) (µg/l) Range (µ/l)
Aluminum 0.1 5–50 3 20–200
Antimony 0.2 1–40 3 20–200
Arsenicb 0.002 0.002–0.02 1 5–100
Barium (p) 0.1 1–20 2 10–200
Beryllium 0.005 0.005–2 0.2 1–30
Cadmium 0.005 0.05–2 0.1 0.5–10
Calcium 0.01 0.2–7 — —
Chromium 0.05 0.5–10 1 5–100
Cobalt 0.05 0.5–5 1 5–100
Copper 0.02 0.2–5 1 5–100
Gold 0.1 0.5–20 1 5–100
Iridium (p) 3 20–500 30 100–1500
Iron 0.03 0.3–5 1 5–100
Lead 0.1 1–20 1 5–100
Magnesium 0.01 0.02–0.5 — —
Manganese 0.01 0.1–3 0.2 1–30
Mercuryc 0.0002 0.0002–0.1 — —
Molybdenum (p) 0.1 1–40 1 3–60
Nickel (p) 0.04 0.3–5 1 5–100
Osmium 0.3 2–100 20 50–500
Palladium (p) 0.1 0.5–15 5 20–400
Platinum (p) 0.2 5–75 20 100–2000
Potassium 0.01 0.1–2 — —
Rhenium (p) 5 50–1000 200 500–5000
Rhodium (p) 0.05 1–30 5 20–400
Ruthenium 0.2 1–50 20 100–2000
Selenium (2)b 0.002 0.002–0.02 2 5–100
Silver 0.01 0.1–4 0.2 1–25
Sodium 0.02 0.03–1 — —
Thallium 0.1 1–20 1 5–100
Tin 0.8 10–300 5 20–300
Titanium (p) 0.4 5–100 10 50–500
Vanadium (p) 0.2 2–100 4 10–200
Zinc 0.005 0.05–1 0.05 0.2–4
Note: The listed furnace values are expected when using a 20-µl injection and normal gas flow except in the cases of As and
Se where gas interrupt is used. The p indicates use of pyrolytic graphite with the furnace procedure.
a
The concentrations shown should be obtainable with any good-quality AAS.
b
Gaseous hydride method.
c
Cold-vapor technique.
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using furnace techniques. In cases where flame AAS does not provide adequate sensitivity, special-
ized furnace procedures are used, such as the gaseous hydride method (see Section 7.6.3 and Chapter
11) for arsenic and selenium, the cold vapor technique (see Section 7.6.4 and Chapter 10) for mer-
cury, and the chelation-extraction procedure (see Section 7.6.2). Table 7.1 contains the detection lim-
its and optimum concentration ranges of atomic absorption spectrophotometers.
7.6 TECHNIQUES IN AAS MEASUREMENT

Atomic absorption is a mature analytical technique. Interferences are well documented and, for the
most part, easy to control. Various atomizer alternatives make atomic absorption one of the most ver-
satile analytical techniques, capable of determining a great number of elements over wide concen-
tration ranges.
7.6.1 DIRECT-ASPIRATION OR FLAME ATOMIC ABSORPTION

SPECTROPHOTOMETRY (FAAS)
In direct-aspiration atomic absorption or flame atomic absorption spectrophotometry (FAAS), a sam-
ple is aspirated and atomized in a flame. A light beam from a hollow cathode lamp (HCL) or an elec-
trodeless discharge lamp (EDL) is directed through the flame into a monochromator and onto a de-
tector that measures the amount of absorbed light. Absorption depends on the presence of free ex-
cited ground-state atoms in the flame. Because the wavelength of the light beam is characteristic of
only the metal being determined, the light energy absorbed by the flame is a measure of the concen-
tration of that metal in the sample. This principle is the basis of AAS. Flames used in the FAAS tech-
nique are discussed in Section 7.3.2, and details of the technique appear in Chapter 8.
7.6.2 CHELATION-EXTRACTION METHOD

Many metals at low concentrations — including Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, Ag, and Zn — can
be determined by the chelation-extraction technique. A chelating agent, such as ammonium pyrroli-
dine dithiocarbamate (APDC), reacts with the metal, forming the metal chelate that is then extracted
with methyl isobutyl ketone (MIBK). An aqueous sample of 100 ml is acidified to a pH 2 to 3 with
1 ml of 4% APDC solution. The chelate is extracted with MIBK by shaking the solution vigorously
for 1 min. If an emulsion formation occurs at the interface of the water and MIBK, use anhydrous
sodium sulfate (Na2SO4). The extract is aspirated directly into the air–acetylene flame. APDC
chelates of certain metals such as Mn are not very stable at room temperature. Therefore, analysis
should commence immediately after extraction.
The chelation-extraction method determines Cr in the hexavalent state. In order to determine total
Cr, the metal must be oxidized with potassium permanganate (KMnO4) at boiling temperature and the
excess KMnO4 is destroyed by hydroxylamine hydrochloride prior to chelation and extraction.
Low concentrations of Al and Be can be determined by chelating with 8-hydroxyquinoline and
extracting the chelates into MIBK and aspirating into an N2O–acetylene flame.
Calibration standards of the metal are similarly chelated and extracted in the same manner, and
the absorbances are plotted against concentrations.
7.6.3 HYDRIDE GENERATION METHOD

Samples are reacted in an external vessel with a reducing agent, usually sodium borohydride.
Gaseous reaction products are then carried to the sampling cell in the light path of the AA spec-
trophotometer. The gaseous reaction products are not free analyte atoms, but rather volatile hydrides.
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To dissociate the hydride gas into free atoms, the sample cell must be heated. The cell is heated by
an air–acetylene flame or with another electricity-driven system. The maximum absorption reading
or peak height is understood as the analytical signal. This technique is discussed in Chapter 11.
7.6.4 COLD VAPOR ATOMIC ABSORPTION SPECTROPHOTOMETER

Because atoms cannot exist in the free ground state at room temperature, heat must be applied to the
sample to break the bonds connecting atoms into molecules. The only notable exception to this gen-
eral rule is mercury. Free mercury atoms can exist at room temperature; therefore, mercury can be
measured by atomic absorption without a heated sample cell. The cold vapor method, which is ap-
plicable to the determination of mercury, is described in Chapter 10.
7.6.5 ELECTROTHERMAL OR GRAPHITE FURNACE ATOMIC ABSORPTION

SPECTROPHOTOMETRY (GRAAS)
When using the furnace technique in conjunction with an atomic absorption spectrophotometer, a
representative aliquot of a sample is placed in the graphite tube in the furnace, evaporated to dryness,
charred, and atomized. As a greater percentage of available analyte atoms is vaporized and dissoci-
ated for absorption in the tube rather than the flame, the use of smaller sample volumes or detection
of lower concentrations of elements is possible.
The principle underlying GrAAS and FAAS is essentially the same, except that a furnace instead
of a flame, respectively, is used to atomize the sample. Radiation from a given excited element is
passed through the vapor containing ground-state atoms of that element. The intensity of the trans-
mitted radiation decreases in proportion to the amount of ground-state element in the vapor. The
metal atoms to be measured are placed in the radiation by increasing the temperature of the furnace,
thereby causing the injected specimen to be volatilized. A monochromator isolates the characteristic
radiation from the hollow cathode lamp or electrodeless discharge lamp, and a photosensitive device
measures the attenuated transmitted radiation. Electrothermal methods generally increase sensitivity.
This technique is described in Chapter 9.
7.7 INTERFERENCE IN AAS TECHNIQUES

When the sample alters one or more steps of the above process (Section 7.3) from the performance
of the standard, interference exists. If the interference is not recognized and corrected, or compen-
sated, the measured concentration will be inaccurate. Interferences in AAS can be divided into two
general categories: nonspectral and spectral.
7.7.1 NONSPECTRAL INTERFERENCES

Nonspectral interferences affect the formation of analyte atoms.
7.7.1.1 Matrix Interference

If the sample is more viscous or has different surface tension characteristics than the standards, the
sample nebulization may be different from the standards. Consequently, the number of the atoms and
thus the absorbance of the standards and samples will not correlate. This situation is known as ma-
trix interference.
For example, negative interference is caused by increased acids or dissolved solids in the sam-
ple. Positive error is caused by the presence of organic solvent in a sample, resulting in increased
L1572_C07 5/23/02 1:26 PM Page 114
absorption. To eliminate this interference, any acid or other reagent added to the sample during prepa-
ration should also be added to the standard and blank in a similar concentration.
7.7.1.1.1 Correction by Standard Addition Method

In this technique, the accurate concentration of the analyte is obtained without the elimination of the
interfering substance. Aliquots of the standard are added to portions of the sample, which allow the
interfering substance in the sample to affect the standard as well.
1. Take equal volumes of aliquot from the sample.

2. Add nothing to the first aliquot.
3. Add a measured amount of standard to the second aliquot. The volume of the standard is
selected to give the approximate concentration of the analyte in the sample.
4. Add twice the volume of the same standard to the third aliquot of the sample.
5. Add three times the first addition of the standard volume to the next aliquot of the sample.
6. Finally, all portions are diluted to the same volume so that the final concentrations of the
original sample constituents are the same in each case. Only the added analyte differs by
a known amount.
The absorbance for all of the solutions must fall within the linear portion of the working curve. If
there is no interference in the sample, a plot of the measured absorbance vs. concentration of the added
standard would be parallel to the aqueous standard calibration. If no interfering substance is present,
the absorbance also increases in the added standards and will be proportional to the analyte in the sam-
ple. Therefore, the result is also a straight line, but because of the interference substance, its slope will
be different from the aqueous standards. Continue the concentration calibration on the abscissa back-
ward from zero and extrapolating the calibration line backward until it intercepts the concentration
axis. This will be the concentration corresponding to the absorbance of the unspiked sample. Thus, the
presence of interference in the sample can be determined easily by the standard addition method. If
the calibration curve of the spiked sample is not parallel with the calibration line of the aqueous stan-
dards, interference is present. The standard addition technique is illustrated in Figure 7.6.
7.7.1.2 Chemical Interferences

During the atomization process, sufficient energy should be available to dissociate the molecular
form of the analyte and create free atoms. If the sample contains a component that forms a thermally
No
interference
Absorbance
Spiked
sample
Aqueous
standards
4.0 2.0 0 2.0 4.0 Concentration
FIGURE 7.6 Standard additions method.

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stable compound with the analyte, complete decomposition is not possible. For example, phosphate
causes this effect in calcium, because calcium phosphate does not totally dissociate in an air–acety-
lene flame.
7.7.1.2.1 Correction by Addition of Excess of

One Chemical Element or Compound
The first solution to chemical interferences is the addition of an excess of one chemical element or
compound that also forms a thermally stable compound with the interfering substance. In the case of
calcium, the addition of lanthanum is the solution. Lanthanum combines with phosphate and allows
the calcium to be completely atomized.
7.7.1.2.2 Correction by the Use of Nitrous Oxide–Acetylene Flame

The second solution to this kind of interference problem is to use a hotter flame. The nitrous
oxide–acetylene flame is considerably hotter than the air–acetylene type and can therefore be used
in interference elimination.
7.7.1.3 Ionization Interference

Most of this type of interference occurs in a hot nitrous oxide–acetylene flame. During the dissocia-
tion process of the molecules, the excess energy causes atoms to easily lose electrons and become
ions. In this case, the excited number of atoms decreases and atomic absorption is reduced, and ion-
ization interference exists.
7.7.1.3.1 Correction by Addition of Ionization Suppressant

Ionization interference can be eliminated with the addition of one element that is very easily ionized,
creating a large number of free electrons in the flame and suppressing ionization of the analyte.
Potassium (K), rubidium (Rb), and cesium (Cs) salts are commonly used as ionization suppressants.
For example, in barium (Ba) determination, adding 1000 to 5000 mg/l potassium (K) to all standards
and samples can eliminate the ionization effect. Recommended additions of ionization suppressants
are listed below.
1. In aluminum (Al), barium (Ba), and chromium (Cr) determination, the addition of 1000
µg/ml (1000 µg/l = 1 mg/l) of potassium (K) is recommended.
a. Preparation of the stock K solution: Dissolve 95 g of potassium chloride (KCl) in
analyte free water and dilute to 1 liter.
b. Add 2 ml of this stock solution into each 100-ml standard and each 100 ml of sample
prior to analysis.
2. In calcium (Ca) and magnesium (Mg) determination, the addition of 1000 µg/ml of lan-
thanum (La) is advised.
a. Preparation of the stock La solution: Dissolve 29 g of lanthanum oxide (La2O3) in 250
ml of HCl concentrate (be careful, reaction is violent!), and dilute to 500 ml with
analyte-free water.
b. Add 2 ml of this stock solution into each 100-ml standard and sample prior to analysis.
3. In molybdenum (Mo) and vanadium (V) determination, the addition of 1000 mg/ml of alu-
minum (Al) is helpful.
a. Preparation of stock solution: Dissolve 139 g of aluminum nitrate nonahydrate
(Al(NO3)3.9H2O) in 150 ml of analyte-free water by heating. After the solution is
completely cool, dilute to 200 ml.
b. Add 2 ml of this stock solution to each 100-ml standard and sample prior to analysis.
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7.7.2 SPECTRAL INTERFERENCES

Spectral interferences are present when the measured light absorption is higher than the absorption
of the analyte. This type of interference is the result of light absorption by a nonanalyte element in
the sample.
7.7.2.1 Background Absorption

In reality, not all of the matrix materials in the sample are 100% atomized. Undissociated matrix mol-
ecules may have broadband absorption spectra, and tiny particles in the flame may scatter light over
a wide wavelength region. This type of absorption covers the atomic absorption wavelength of the
analyte, and background absorption occurs.
7.7.2.1.1 Continuous Source Background Correction

To eliminate this type of interference, the background absorption must be measured and subtracted
from the total absorption to verify the analyte’s absorption. The lack of accuracy of this method led
to the development of a more convenient technique called continuous source background correc-
tion, which automatically measures and compensates for any background absorption. This method
incorporates a continuum light source in the optical system. Light from both the primary and con-
tinuum lamps are combined and pass through the flame and monochromator and reach the detector.
The instrument itself separates the detector’s response. The continuum source signal can be sub-
tracted electronically from the primary signal source, which contains the sum of the background and
atomic absorption signals. The displayed absorbance and concentration will correspond to the dif-
ference of the absorbance of the lamps. Figure 7.7 shows how background absorption is eliminated
by using this technique.
7.7.2.1.2 Zeeman Background Correction

The other method for correcting background absorbance is the Zeeman background correction. The
principle of this technique is that the energy levels of an atom change when the atom is placed in a
strong magnetic field. The spectrum of the atom, which is a measure of energy levels, also changes,
but the background absorption is usually unaffected by the magnetic field. When an atom is placed
in a magnetic field and its atomic absorption is observed with a polarized light (polarized light vi-
brates in only one plane, in contrast to ordinary light, which vibrates in all planes, as can seen in
Appendix G), the normal single-line atomic absorption is split into two components symmetrically
displaced about the normal position, as seen in Figure 7.8. In the Zeeman background correction, a
Continuum
source
Monochromator
Detector
Primary
source
FIGURE 7.7 Continuum source background corrector.

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No FIGURE 7.8 Zeeman effect.

Magnetic
Field
νo
Normal
Zeeman
Pattern
σ+ νo σ+
Absorption
Line
Background
Magnetic
Field Off
Emission
Line
Absorption
νo
Lines
Magnetic σ- σ+
Field On Background
Emission
FIGURE 7.9 Zeeman effect background correction. Line
νo
magnetic field is placed around the atomizer and makes alternating absorption measurements with
the magnet off and on. At the “magnet off” position, the uncorrected total absorbance can be meas-
ured, and in the “magnet on” position, the background absorbance reading is made, as seen in
Figure 7.9. The comparison automatically made by the instrument to compensate for background
correction is similar to the continuum source technique. In the Zeeman background correction, the
emission profile of the light source is identical in both AA and background measurements. As a re-
sult, most complex structured background situations can be accurately corrected with the Zeeman
background correction.
7.7.3 SUMMARY OF INTERFERENCES

7.7.3.1 Nonspectral Interference
1. Matrix interference: Sample nebulization is different from standards, so the absorbance of
samples is not correlated with standards. This type of interference can be eliminated by
special care and selection of the sample preparation technique, or by using the standard
addition method.
2. Chemical interference: If the sample contains a component that forms a thermally stable
component with the analyte, it is not able to complete decomposition. It can be clarified
by the addition of an excess of an appropriate chemical element or compound, or by
changing to a hotter nitrous oxide-acetylene flame.
3. Ionization interference: In the hot nitrous oxide–acetylene flame during the dissociation
process, atoms lose electrons and become ions. Consequently, the number of atoms and
thus the atomic absorptions are reduced. The interference may be reduced by adding an
excess of an element (called a suppressant) that is very easily ionized and suppresses the
ionization of the analyte.
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7.7.3.2 Spectral Interference

The measured absorption is higher than the absorption of the analyte, caused by the light absorption
by a nonanalyte element in the sample. This type of interference is called background absorption,
and is compensated by instrument correction, such as the continuum source background correction
and Zeeman background correction techniques.
7.8 SAFETY IN AAS WORK

Important safety considerations regarding the use of AAS equipment are summarized in the follow-
ing sections.
7.8.1 FLAMMABILITY OF ACETYLENE

Acetylene, a common fuel in AAS work, is flammable. Its flammability poses a safety problem.
7.8.2 COMBUSTION PRODUCTS

During equipment operation, combustion products can easily pollute the laboratory atmosphere. For
this reason, an independently vented fume hood is placed above the burner to remove burned and un-
burned fuel from the area as illustrated in Figure 7.10.
7.8.3 FLASHBACKS
Flashbacks are minor explosions due to improperly mixed fuel and air. Some specific causes of flash-
backs are:
1. Air being drawn back through the drain hole in the mixing chamber of the premix burner.
This problem can be avoided by connecting a 6-ft-long tube to the drain hole and forming
the tube into a loop, which is then filled with water. The other end is then placed into a con-
tainer of water (see Figure 7.10).
2. Shutting off all air to the burner before the fuel has been shut off. The solution here is
proper operation and proper instruction of operators.
3. Improper proportioning of the fuel air while adjusting the fuel or airflow rate. The solu-
tion to this problem is the same as in (2).
Because of the danger of flashbacks, safety glasses must be worn at all times while operating the in-
strument. General laboratory safety considerations are discussed in Chapter 19.
7.9 QUALITY CONTROL

See Chapter 13 for detailed quality control procedures to be followed during analysis.
7.10 MAINTENANCE OF AA SPECTROPHOTOMETERS

Constant care and routine maintenance are the secret for maintaining proper working conditions of
laboratory instruments. Maintenance activities for each instrument are found in the manufacturer’s
manual. A written maintenance schedule for each instrument must be available. The laboratory must
have a maintenance expert on staff or contract with the vendor to provide a specialist for maintenance
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Fume hood
Liquid in "trap"
in drain line
Waste solution
FIGURE 7.10 AA instrument showing fume hood and drain line.
activities. Routine maintenance activities are based on recommendations of the manufacturer of each
type and model. Maintenance frequency may also change according to the workload and the type of
samples analyzed. Scheduling of maintenance activities by AAS type is presented in Table 7.2.
7.11 AAS PERFORMANCE CHECKS

Performance checks should occur every time a different metal is analyzed as part of the analytical
procedure. The performance check is an indicator of deterioration of the lamps or the spectropho-
tometer and reveals the instrument’s optimal operating condition. Performance is measured via a
“sensitivity check standard” based on a concentration specific to the method for each metal. The ab-
sorbance of this standard should be 0.200. If the absorbance differs by more than ±10%, the instru-
ment is not performing correctly and has to be corrected. Metal concentrations used in sensitivity
check data for flame and graphite techniques are presented in Tables 8.1 and Table 9.4, respectively.
7.12 SAMPLE COLLECTION AND SAMPLE PREPARATION

Collection and preparation of environmental samples for analysis using atomic absorption and
atomic emission spectrophotometers are discussed in Chapters 14 and 15.
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TABLE 7.2
Maintenance of Atomic Absorption Spectrophotometer
Instrument Type Maintenance Activity Frequency

UV/Vis Check lamp alignment W
Replace lamp AN
Clean windows Q (I) (C)
Clean sample compartment D
Clean cuvettes after use D
IR Clean sample cell D

Clean windows M
Change dessicant Q
Check gas leakage D
AA flame Clean nebulizer D

Clean burner head D
Check tubing, pump, and lamps D
Clean quartz windows W
Check electronics SA (I) (C)
Check optics A (I) (C)
AA graphite Check graphite tube D

Flush autosampler tubing D
Clean furnace housing and injector tip W
Note: D = daily; W = weekly; M = monthly; Q = quarterly; SA = semiannually; A = annually; AN = as

needed; I = instrumentation specialist; C = on contract.
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Direct Aspiration or
8 Flame Atomic Absorption
Spectrometry (FAAS)
8.1 PRINCIPLE
Flame atomic absorption spectrometry is a rapid and precise method of analysis. In this atomic ab-
sorption spectrometry technique (see Section 7.6.1), the sample is vaporized and atomized in a high-
temperature flame. Atoms of the analyte element absorb light of a specific wavelength from a hollow
cathode lamp (HCL), passing through the flame. The amount of energy absorbed by these atoms is
measured and is proportional to the number of atoms in the light path. A light beam is directed
through the flame into a monochromator and onto a detector that measures the amount of light ab-
sorbed by the atomized element in the flame. The amount of energy at the characteristic wavelength
absorbed in the flame is proportional to the concentration of the element in the sample over a limited
concentration range. Table 8.1 shows the FAAS concentration ranges.
Determinations of analyte concentrations in a milligram-per-liter concentration region are routine
for most elements. However, trace metal analyses at microgram-per-liter and nanogram-per-liter levels
are also needed. Because the thermal energy from the flame is responsible for producing the absorbing
species, flame temperature is an important parameter governing the flame process. The two premixed
flames used almost exclusively for atomic absorption are air–acetylene (2125–2400°C) and nitrous
oxide–acetylene (2000–2800°C).
While the air–acetylene flame is satisfactory for most elements determined by atomic absorption,
the hotter nitrous oxide–acetylene flame is required for many refractory-forming elements. The ni-
trous oxide–acetylene flame is also effective in the control of some types of interferences.
8.2 DIRECT AIR–ACETYLENE FLAME METHOD

Because the thermal energy from the flame is responsible for producing the absorbing species, flame
temperature is an important parameter governing the flame process. Flames used in the AAS tech-
nique are discussed in Section 7.3.2. The air–acetylene flame is satisfactory for most elements de-
termined by atomic absorption, including Sb, Bi, Cd, Cs, Cr, Co, Cu, Au, Ir, Fe, Pb, Li, Mg, Mn, NI,
Pa, Pt, K, Rh, Ru, Ag, Na, Sr, Ta, Sn, and Zn.
8.2.2 INSTRUMENTATION
See Section 7.3.
121
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TABLE 8.1
Atomic Absorption Concentration Ranges, FAAS Technique
Instrument Optimum
Wavelength Flame Detection Sensitivity Concentration
Element (nm) Gas Limit (mg/l) (mg/l) Range (mg/l)
Ag 328.1 A–Ac 0.01 0.06 0.1–4
Al 309.3 N–Ac 0.1 1 5–50
Au 242.8 A–Ac 0.01 0.25 0.5–20
Ba 553.6 N–Ac 0.03 0.4 1–20
Be 234.9 N–Ac 0.005 0.03 0.05–2
Bi 223.1 A–Ac 0.06 0.4 1–50
Ca 422.8 A–Ac 0.03 0.08 0.2–20
Cd 228.8 A–Ac 0.02 0.025 0.05–2
Co 240.7 A–Ac 0.03 0.2 0.5–10
Cr 357.9 A–Ac 0.02 0.1 0.2–10
Cs 852.1 A–Ac 0.02 0.3 0.5–15
Cu 324.8 A–Ac 0.01 0.1 0.20–10
Fe 248.3 A–Ac 0.02 0.12 0.3–10
Ir 264.0 A–Ac 0.6 8 —
K 766.5 A–Ac 0.005 0.04 0.1–2
Li 670.8 A–Ac 0.002 0.04 0.1–2
Mg 285.2 A–Ac 0.0005 0.007 0.2–2
Mn 279,5 A–Ac 0.01 0.05 0.1–10
Mo 313.3 N–Ac 0.1 0.5 1–20
Na 589.0 A–Ac 0.02 0.015 0.03–1
Ni 232.0 A–Ac 0.02 0.15 0.3–10
Os 290.9 N–Ac 0.08 1 —
Pba 283.3 A–Ac 0.05 0.5 1–20
Pt 265.9 A–Ac 0.1 2 5–75
Rh 343.5 A–Ac 0.5 0.3 —
Ru 349.9 A–Ac 0.07 0.5 —
Sb 217.6 A–Ac 0.07 0.5 1–40
Si 251.6 N–Ac 0.3 2 5–150
Sn 224.6 A–Ac 0.8 4 10–200
Sr 460.7 A–Ac 0.03 0.15 0.3–5
Ti 365.3 N–Ac 0.3 2 5–100
V 318.4 N–Ac 0.2 1.5 2–100
Zn 213.9 A–Ac 0.05 0.2 0.05–2
Note: A–Ac = air–acetylene; N–Ac = nitrous oxide–acetylene.
a
The more sensitive 217.0-nm wavelength is recommended for instruments with background correction capabilities.
8.2.3 REAGENTS
8.2.3.1 Air
The air used should be cleaned and dried through a suitable filter to remove oil, water, and other for-
eign substances. Sources include a compressor or commercially bottled gas.
8.2.3.2 Acetylene
The acetylene used should be a standard commercial grade. Acetone, which is always present in acety-
lene cylinders, can be prevented from entering and damaging the burner head by replacing a cylinder
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Direct Aspiration or Flame Atomic Absorption Spectrometry (FAAS) 123
when its pressure has fallen to 689 kPa (100 psi) acetylene. Because of differences among makes and
models of AASs, it is not possible to formulate measurements applicable to every instrument.
8.2.3.3 Metal-Free Water

Use metal-free water for preparing all reagents and calibration standards and as dilution water.
Prepare metal-free water by deionizing and distilling, redistilling, or sub-boiling tap water. Always
check laboratory pure water to determine whether the element of interest is present in trace amounts.
Note: If the source water contains Hg or other volatile metals, single or redistilled water may not
be suitable for trace analysis, because these metals remain in distilled water. In such cases, use sub-
boiling to prepare metal-free water.
8.2.3.4 Stock Metal Solutions

Stock metal solutions are commercially available or can be prepared according to recipes in
Appendix H.
8.2.4 OPERATION
Because of differences among makes and models of AASs, it is not possible to formulate instruc-
tions applicable to every instrument. Follow the manufacturer’s instructions, but in general proceed
as follows:
1. Install hollow cathode lamp for the desired metal.

2. Set wavelength dial as specified by the analytical methodology (see Table 8.1).
3. Set slit width according to manufacturer’s suggested setting.
4. Turn on instrument, apply the hollow cathode lamp current suggested by the manufacturer,
and let the instrument warm up until energy source stabilizes, usually about 10 to 20 min.
5. Readjust current if necessary after warm-up. Adjust wavelength dial until optimum energy
gain is obtained.
6. Align lamp in accordance with manufacturer’s instructions.
7. Install suitable burner head, and adjust its position. A 10-cm, single-slot burner head is
recommended for air–acetylene flames.
8. Turn on air, and adjust flow rate according to manufacturer’s instructions to give maxi-
mum sensitivity for the metal being measured.
9. Turn on acetylene and adjust flow rate to value specified.
10. Ignite flame and let it stabilize for a few minutes.
11. Aspirate blank and zero instrument.
12. Aspirate a standard solution and adjust aspiration rate of nebulizer to obtain maximum
sensitivity.
13. Adjust burner both vertically and horizontally to obtain maximum response.
14. Aspirate blank again and re-zero instrument.
15. Aspirate a standard with a concentration near the middle of the linear range and record
absorbance.
16. The instrument is now ready to operate.
17. When analyses are finished, extinguish flame by turning off acetylene first and then air.
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8.2.5 STANDARDIZATION
1. Select at least three concentrations of each standard metal solution to bracket expected metal
concentration of sample. (See Table 8.1 for the optimum concentration ranges of metals.)
3. Aspirate each standard and record absorbances. Prepare the calibration curve (Section
6.6). For instruments equipped with direct concentration readout, this step is unnecessary.
Preparation of standards and complete calibration processes are discussed in Section 6.6.
Calibrate Ca and Mg based on concentration of standards before dilution with lanthanum solu-
tion; Fe and Mn based on original concentration of standards before dilution with calcium solution;
and Cr based on original standards before addition of H2O2. See methodologies for determining these
metals in Chapter 18.
8.2.6 SAMPLE ANALYSIS

1. Rinse the nebulizer by aspirating water with 1.5 ml of concentrated HNO3/l.
2. Aspirate blank and zero instrument. Analyze samples.
8.2.7 CALCULATIONS
1. Calculate from calibration curve, or read directly from instrument the concentration in
milligrams or micrograms per liter according to calibration.
2. If the sample has been diluted, multiply concentration readout by the appropriate dilution
factor.
3. If the sample has been concentrated, divide concentration readout by appropriate concen-
tration factor.
8.3 DIRECT NITROUS OXIDE–ACETYLENE FLAME METHOD

The hotter nitrous oxide–-acetylene flame (2600–2800°C) is required for many refractory-forming
elements. The nitrous oxide–acetylene flame is also effective in the control of some types of inter-
ference. This method is applicable to the determination of Al, Ba, Be, Mo, Os, Re, Si, Th, Ti, and V.
8.3.2 APPARATUS
Use atomic absorption spectrophotometer and associated equipment. See Section 7.3.
8.3.2.1 Nitrous Oxide Burner Head

Use special burner head as suggested in the manufacturer’s manual. At roughly 20-min intervals of
operation, it may be necessary to dislodge the carbon crust that forms along the slit surface with a
carbon rod or appropriate alternative. Usually a special 5-cm head is required when using a nitrous
oxide–acetylene flame. Burner heads are discussed in Section 7.3.3.
8.3.2.2 T-Junction Valve

Use a T-junction valve or other switching valve for rapidly changing from nitrous oxide to air, so that
the flame can be turned on or off with air as the oxidant to prevent flashbacks.
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8.3.3 REAGENTS
8.3.3.1 Air
See Section 8.2.3.
8.3.3.2 Acetylene
See Section 8.2.3.
8.3.3.3 Nitrous Oxide

Nitrous oxide is commercially available in cylinders. Fit the nitrous oxide cylinder with a special
nonfreezable regulator, or wrap a heating coil around an ordinary regulator to prevent flashback at
the burner caused by reduction in nitrous oxide flow through a frozen regulator. Some AASs have au-
tomatic gas control systems that will shut down a nitrous oxide flame safely in the event of a reduc-
tion in nitrous oxide flow rate.
8.3.3.4 Metal-Free Water

See Section 8.2.3.
8.3.3.5 Potassium Chloride Solution

Dissolve 250 g of KCl and dilute to 1000 ml with water.
8.3.3.6 Aluminum Nitrate Solution

Dissolve 139 g of Al(NO3)3.9H2O in 150 ml of water. Acidify slightly with concentrated HNO3 to
prevent hydrolysis and precipitation. Warm to dissolve completely. Cool and dilute to 200 ml.

These solutions are commercially available or can be prepared according to recipes in Appendix H.
8.3.4 OPERATION
Instrument operation follows the air–acetylene flame method, as discussed in Section 8.2.4. After
steps 1 to 6, proceed as follows:
7. After adjusting wavelength, install a nitrous oxide burner head.

8. Turn on acetylene (without igniting flame) and adjust flow rate according to value speci-
fied by manufacturer for a nitrous oxide–acetylene flame.
9. Turn off acetylene.
10. With both air and nitrous oxide supplies turned on, set T-junction valve to nitrous oxide
and adjust flow rate according to manufacturer’s specifications.
11. Turn switching valve to the air position and verify that the flow rate is the same.
12. Turn acetylene on and ignite to a bright yellow flame.
13. With a rapid motion, turn switching valve to nitrous oxide. The flame should have a red
cone above the burner. If it does not, adjust fuel flow to obtain red cone. After nitrous oxide
flame has been ignited, let burner come to thermal equilibrium before starting analysis.
14. Atomize water containing 1.5 ml of concentrated HNO3 per liter and check aspiration rate.
Adjust if necessary to a rate between 3 and 5 ml/min.
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15. Aspirate standard of desired metal with concentration near the midpoint of the optimum
concentration range and adjust burner (both vertically and horizontally) in light path to ob-
tain maximum response. The instrument is ready for analysis.
16. To extinguish flame, turn switching valve from nitrous oxide to air and turn off acetylene.
This procedure eliminates the danger of flashback that may occur on direct ignition or
shutdown of nitrous oxide and acetylene.
1. Select at least three concentrations of standard metal solution to bracket expected metal
concentration of sample. See Table 8.1 for optimum concentration ranges of metals.
3. Aspirate each standard and record absorbances. Prepare calibration curve (Section 6.6).
For instruments equipped with direct concentration readout, this step is unnecessary.
Preparation of standards and complete calibration processes are discussed in Section 6.6.
For 100 ml of Al, Ba, and Ti standards, add 2 ml of KCl solution (dissolve 250 g of KCl and di-
lute to 1000 ml). For 100 ml of Mo and V standards, add 2 ml of Al(NO3)3.9H2O solution. (Dissolve
139 g of Al(NO3)3.9H2O in 150 ml of water, acidify slightly with concentrated HNO3, and warm to
dissolve completely. Cool and dilute to 200 ml.)
Most modern instruments are equipped with microprocessors and digital readouts that permit
calibration in the direct concentration range.
8.3.6 ANALYSIS OF SAMPLES

1. After standardization, rinse atomizer by aspirating water with 1.5 ml of concentrated
HNO3 per liter and zero instrument.
2. Analyze samples. When analyzing Al, Ba, and Ti, add 2 ml of KCl solution to a 100-ml
sample before analysis. When analyzing Mo and V, add 2 ml of Al(NO3)3 solution to a
100-ml sample.
8.3.7 CALCULATIONS
See Section 8.2.7.
8.4 INTERFERENCES, SAFETY, AND QUALITY CONTROL REQUIREMENTS

IN FAAS
See Sections 7.7, 7.8, and 7.9, respectively.
8.5 MAINTENANCE OF FAA SPECTROPHOTOMETER

Maintenance activities for the FAAS are listed in Table 8.2.
8.6 PERFORMANCE CHECK OF FAA SPECTROPHOTOMETER

Performance of the AAS is checked every time a different metal is analyzed. The performance check
is an indicator of deterioration of the lamps or the spectrophotometer and reveals the optimal oper-
ating condition of the instrument. Performance is measured by a “sensitivity check standard” based
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TABLE 8.2
Maintenance of FAAS
Maintenance Activity Frequency
Clean bebulizer D
Clean burner head D
Check tubing, pump, and lamps D
Clean quartz windows W
Checks optics A (I) (C)
Note: D = daily; W = weekly; SA = semiannually; A = annually; I =

instrumentation specialist; C = on contract.
on a concentration specific to the method for each metal. The absorbance of this standard should be
0.200. If it differs by more than 10%, the instrument is not performing correctly and has to be cor-
rected. Metal concentrations used in performance checks for the FAAS technique are presented in
Table 8.3. Standard conditions for the FAAS technique are summarized in Table 8.4.
TABLE 8.3
FAAS Performance Check
Element Concentration of Sensitivity Standard (mg/l)

Aluminum (Al) 50
Antimony (Sb) 25
Barium (Ba) 20
Beryllium (Be) 1.5
Calcium (Ca) at 422.7 nm 4.0
Calcium (Ca) at 287.4 nm 60
Cadmium (Cd) at 228.8 nm 1.5
Cadmium (Cd) at 368.4 nm 850
Cobalt (Co) 7.0
Chromium (Cr) 4.0
Copper (Cu) 4.0
Iron (Fe) 5.0
Lead (Pb) 20
Potassium (K) 2.0
Magnesium (Mg) 0.3
Manganese (Mn) 2.5
Molybdenum (Mo) 30
Nickel (Ni) 7.0
Silicon (Si) 100
Sodium (Na) 0.5
Strontium (Sr) 5.0
Tin (Sn) 150
Titanium (Ti) 80
Thallium (Ta) 30
Tungsten (W) 450
Zinc (Zn) 1.0
Zirconium (Zr) 300
Note: Performance of the FAA should be checked every time a metal is analyzed by
using a sensitivity check standard. The sensitivity check data here pertain to the metal
concentration (mg/l) in aqueous solution, which will give a reading of approximately
0.20 absorbance units.
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TABLE 8.4
Standard Conditions for Flame AAS
Wavelength Optimum Sensitivity Detection Addition of
Metal Fuel Oxidant SBW (nm) (nm) Range (mg/l) Check (mg/l) Limit (mg/l) Suppressant
Ag Ac–air 0.7 328.1 0.1–4 2.5 0.01 a
Al Ac–N2O 0.7 324.7 5–50 50.0 0.1 —

Ba Ac–N2O 0.4 553.6 1.0–20 20.0 0.1 2 ml KCL per
100-ml
sample
Be Ac–N2O 0.7 234.9 0.05–2 1.5 0.005 —
Cd Ac–air 0.7 228.8 0.05–2 1.5 0.005 —
Ca Ac–N2O 0.7 422.7 0.2–7 4.0 0.01 1 ml LaCl3 per
10-ml sample
Cr Ac–N2O 0.7 357.9 0.5–10 4.0 0.05 2 ml KCL per

100-ml
sample
Co Ac–air 0.2 240.7 0.5–5 7.0 0.05 —

Cu Ac–air 0.7 324.7 0.2–5 4.0 0.02 —
Fe Ac–air 0.2 248.3 0.3–5 5.0 0.03 —
K Ac–air 1.4 766.5 0.1–2 2.0 0.01 a
Mg Ac–air 0.7 285.2 0.02–0.05 0.3 0.001 1 ml LaCl3 per

10-ml sample
Mn Ac–air 0.2 279.5 0.1–3 2.5 0.01 a
Mo Ac–N2O 0.2 313.3 1–40 30 0.1 —

Ma Ac–air 0.4 589.0 0.03–1 0.5 0.002 a
Ni Ac–air 0.2 232.0 0.3–5 7.0 0.04 —

Pb Ac–air 0.7 283.3 1–20 20 0.1 a
Sb Ac–air 0.2 217.6 1–40 25 0.2 —

Si Ac–N2O 0.2 251.6 — 100 — —
Sn Ac–N2O 0,7 286.3 10–300 150 0.8 —
Sr Ac–N2O 0.4 460.7 — 5.0 — —
Ti Ac–Air 0.7 276.8 1–20 30 0.1 a
V Ac–N2O 0.7 318.4 2–200 90 0.2 2 ml Al(NO3)2

per 100-ml
sample
Zn Ac–air 0.7 213.9 0.05–1 1.0 0.005 a

Note: Potassium chloride (KCl) solution: Dissolve 95 g of KCl in analyte-free water and dilute to 1 liter. Lanthanum chloride
(LaCl3) solution: Dissolve 29 g of La2O3 in 250 ml of concentrated HCl (be careful, because reaction is violent!), and dilute to
500 ml with analyte-free water. Aluminum nitrate (Al(NO3)2) solution: Dissolve 139 g of aluminum nitrate nonahydrate
(Al(NO3)2.9H2O) in 150 ml of analyte-free water. Heat. After dissolution, cool to room temperature, and dilute to 200 ml.
Suppressant should be added to the blanks, standards, and samples. Addition of alkali salt is recommended to control ioniza-
tion. Aluminum is added to improve sensitivity and linearity. Lanthanum is added to improve sensitivity.
a
The use of an impact bead will improve sensitivity by about 2%.
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Graphite Furnace Atomic

9 Absorption Spectrometry
9.1 GENERAL DISCUSSION

9.1.1 APPLICATION
An atomic absorption spectrophotometer equipped with a graphite furnace or an electrically heated
atomizer, instead of a standard burner head, offers better sensitivity and a much lower detection limit
compared to the flame method (see Chapter 8). The sensitivity of electrothermal AAS or graphite fur-
nace AAS (GrAAS) makes it ideal for trace metals analysis. The GrAAS determination of most
metallic element sensitivities and detection limits is 20 to 1000 times better than that of conventional
flame techniques. Many elements can be determined at concentrations as low as 1.0 µg/l.
The GrAAS technique is subject to more interference than the FAA procedure and requires more
analysis time. However, extensive studies of the furnace technique combined with the development
of improved instrumentation have changed the GrAAS into a highly reliable, routine technique for
trace metals analysis. It is also much more automated than the other techniques in this field. The en-
tire process is automated once the sample has been introduced and the furnace program initiated.
With the use of automatic samplers, a completely unattended operation is possible.
An additional benefit of the GrAA technique is the use of microliter sample sizes. Routine de-
termination at the microgram-per-liter (ppb) level for most elements makes it ideal for environmen-
tal applications, but it is also suitable for biological and geological samples, and many clinical analy-
ses. The graphite furnace method can determine most elements, measured by atomic absorption, in
a wide variety of matrices.
9.1.2 PRINCIPLE
Electrothermal atomic absorption spectroscopy (GrAAS) is based on the same principle as direct-
flame atomic absorption spectroscopy (FLAAS). In the GrAAS technique, a tube of graphite is lo-
cated in the sample compartment of the AAS, with the light path passing through it. A small volume
of sample solution is quantitatively placed into the tube, normally through a sample injection hole lo-
cated in the center of the tube wall. The tube is heated through a programmed temperature sequence
until finally the analyte present in the sample is dissociated into atoms. The resultant ground-state
atomic vapor absorbs monochromatic radiation from the source. As atoms are created and diffuse out
of the tube, the absorbance rises and falls in a peak-shaped signal. The peak height or integrated peak
area is used as the analytical signal for quantitation. The detection limits, optimum concentration
ranges, and wavelengths used are presented in Table 9.1. For a comparison with the flame AA tech-
nique, see Table 8.1. (Sensitivity, detection limits, and optimum concentration range are discussed in
Sections 7.5.3, 7.5.4, and 7.5.5, respectively).
129
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Use of the stabilized temperature platform furnace (STPF) technique also offers significant in-
terference reduction with improved sensitivity. See Section 9.5 for a detailed discussion of the STPF.
Sensitivity changes with sample tube age. Discard graphite tubes when significant variations in
sensitivity or poor reproducibility are observed. The use of high acid concentrations, brine samples,
and matrix modifiers (see Sections 9.3.2 and 9.4.1) often drastically reduce tube life. Use of the L’vov
platform (Section 9.4.2) in such situations is preferable.
9.2 APPARATUS
9.2.1 ATOMIC ABSORPTION SPECTROPHOTOMETER
A single- or dual-channel or single- or double-beam instrument has a grating monochromator, pho-
tomultiplier detector, adjustable slits, and a wavelength range of 190 to 800 nm, and is equipped with
a strip-chart recorder (see Section 9.2.5). The instrument must have background correction capabil-
ity.
9.2.2 BURNER
The burner recommended by the instrument manufacturer should be used. For certain elements, the
nitrous oxide burner is required.
9.2.3 HOLLOW CATHODE LAMPS

Single-element lamps are preferred but multielement lamps are also used. Electrodeless discharge
lamps (EDLs) may also be used when available (Section 7.3.1).
9.2.4 GRAPHITE FURNACE

Any furnace device capable of reaching the specified temperatures is satisfactory. Use an electrically
heated device with electronic control circuitry designed to carry a graphite tube through a heating
program that provides sufficient thermal energy to atomize the element of interest. Fit the furnace
into the sample compartment of the spectrometer in place of the conventional burner assembly. Use
argon as a purge gas to minimize oxidation of the furnace tube and to prevent the formation of metal-
lic oxides. The graphite furnace is made up of three major components: atomizer, power supply,
and programmer.
9.2.4.1 Atomizer
The atomizer is located in the sampling compartment of the AAS. The basic graphite furnace atom-
izer is composed of the following components: graphite tube, electrical connection, water-cooled
housing, and inert gas purge control. Figure 9.1 illustrates the graphite furnace atomizer.
9.2.4.1.1 Graphite Tube

Normally the graphite tube is the furnace’s heating element. This cylindrical tube is aligned hori-
zontally in the optical path of the spectrophotometer and serves as the sampling cell. A few micro-
liters (5–50 µl) of sample are measured and dispensed through a hole in the center of the tube wall
or graphite platform. Use graphite tubes with L’vov platforms to minimize interference and to im-
prove sensitivity.
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Graphite Furnace Atomic Absorption Spectrometry 131
Internal External
External Internal
Gas Flow Gas Flow
Gas Flow Gas Flow
Graphite
Window Assembly
Cooling
Ring
Light Beam
Graphite
Graphite Tube
Contacts
External External
Gas Flow Gas Flow
FIGURE 9.1 Graphic furnace atomizer.
9.2.4.1.2 Electrical Connection

The tube is held in place between two graphite contact cylinders that provide the electrical connec-
tion. An electrical potential applied to the contacts causes current to flow through the tube, which
heats the tube and the sample.
9.2.4.1.3 Water-Cooled Housing

The entire assembly is mounted within an enclosed water-cooled housing. Quartz windows at each
end of the housing allow light to pass through the tube.
9.2.4.1.4 External and Internal Gas Flows

The heated graphite is protected from air oxidation by the end windows and two streams of argon. An
external gas flow surrounds the outside of the tube, and a separately controlled internal gas flow purges
the inside of the tube. During atomization, the internal gas flow is reduced or, preferably, completely
interrupted. This maximizes sample residence time in the tube and increases the measurement signal.
9.2.4.2 Power Supply

The power supply controls the electrical power of the graphite tube.
9.2.4.3 Programmer
The temperature of the tube is controlled by a user-specified temperature program. Through the pro-
grammer, the operator selects the sequence of the temperature vs. time during atomization. The pro-
grammer also controls the internal inert gas flow rate and certain spectrometer functions.
9.2.5 STRIP-CHART RECORDER

A recorder is recommended for furnace work to generate a permanent record and as a means to eas-
ily recognize problems, such as drift, incomplete atomization, losses during charring, changes in sen-
sitivity, peak shape, and so on.
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9.2.6 WATER SUPPLY FOR COOLING

Cool with tap water flowing at 1 to 4 l/min or use a recirculating cooling device.
9.2.7 SAMPLE DISPENSERS

Use microliter pipets with disposable tips (5–100 ml) or an automatic sampling device designed for the
specific instrument. Pipet tips should be checked prior to use as a possible source of contamination.
9.3 ANALYSIS BY GRAPHITE FURNACE SPECTROPHOTOMETER

9.3.1 SAMPLE PRETREATMENT
See Chapter 15.
9.3.2 REAGENTS
9.3.2.1 Metal-Free, Reagent-Grade Water
Use metal-free water for preparing all reagents and calibration standards and as a dilution water.
Always check deionized or distilled water to determine whether the element of interest is present in
trace amounts. If the source water contains Hg or other volatile metals, distilled or redistilled water
may not be suitable for trace analysis because these metals remain in distilled water. In such cases,
use sub-boiling to prepare metal-free water.
9.3.2.2 Hydrochloric Acid (HCl)

Both concentrate and 1:1 dilution are used.
9.3.2.3 Nitric Acid (HNO3)

Both concentrate and 1:1 dilution are used.

These solutions are commercially available or can be prepared according to recipes in Appendix H.
9.3.2.5 Matrix Modifiers
9.3.2.5.1 Ammonium Nitrate, 10% (w/v)

Dissolve 100 g of NH4NO3 and dilute to 1000 ml with reagent-grade water.
9.3.2.5.2 Ammonium Phosphate, 40% (w/v)

Dissolve 40 g of (NH4)2HPO4 and dilute to 100 ml with reagent-grade water.
9.3.2.5.3 Calcium Nitrate, 20,000 mg Ca per Liter

Dissolve 11.8 g of Ca(NO3)2.4H2O and dilute to 100 ml with reagent-grade water.
9.3.2.5.4 Nickel Nitrate, 10,000 mg Ni per Liter

Dissolve 49.56 g of Ni(NO3)2.6H2O and dilute to 1000 ml with reagent-grade water.
9.3.2.5.5 Phosphoric Acid, 10% (v/v)

Dilute 10 ml of H3PO4 concentrate to 100 ml with reagent-grade water.
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9.3.2.6 Metal-Free Seawater or Brine

1. Fill a 1.4-cm × 20-cm borosilicate glass column to within 2 cm of the top with purified
chelating resin (see Section 9.3.2.7 below).
2. Elute resin with successive 50-ml portions of 1N HCl, metal-free water, 1N NaOH, and
metal-free water at the rate of 5 ml/min just before use.
3. Pass salt water or brine through the column at a rate of 5 ml/min to extract trace metals
present. Discard the first 300 ml of eluate.
9.3.2.7 Chelating Resin

1. Purify 100- to 200-mesh (Chelex 100 or equivalent) by heating at 60°C in 19N NaOH for
24 h.
2. Cool resin and rinse ten times each with alternating portions of 10N HCl, metal-free water,
1N NaOH, and metal-free water.
9.3.3 INSTRUMENT OPERATION

1. Mount and align the furnace device according to the manufacturer’s instructions.
2. Turn on the instrument and strip-chart recorder.
3. Select the appropriate light source and adjust the recommended electrical setting.
4. Select the appropriate wavelength and set all conditions according to the manufacturer’s
instructions, including background correction. Background correction is important when
elements are determined at short wavelengths or when the sample has a high level of dis-
solved solids. In general, background correction is usually not necessary at wavelengths
longer than 350 nm. Above 350 nm, deuterium arc background correction is not useful and
other types of correction must be used.
5. Through the programmer, enter a sequence of selected temperature vs. time to carefully
dry, pyrolyze, and finally, atomize the sample. The program may also include settings for
the internal inert gas flow rate and, in some cases, the selection of an alternate gas.
9.3.4 MULTI-STEP TEMPERATURE PROGRAM

1. Drying step: After the sample is placed in the furnace, it must be dried at a sufficiently low
temperature to avoid sample splattering. Temperatures of 100 to 120°C are common for
aqueous samples. During the drying step, the internal gas flow is left at a 300-ml/min value
to purge out the vaporized solvent.
a. Ramp time is a variable time over which the temperature is increased. A longer ramp
time provides a slower, more gentle increase in heat. Ramp time is usually 1 sec with
the platform, and longer when the sample is atomized from the tube wall.
b. Hold time is the time that the sample is held at the selected temperature until dry.
Because only a few microliters of sample are used, it is usually less than a minute.
2. Pyrolysis step: The temperature is increased as high as possible to volatilize the compo-
nents, but low enough to prevent loss of the analyte. Temperature selection depends on the
nature of the analyte and the matrix.
3. Cool-down or preatomization step: Cool the furnace prior to atomization.
4. Atomization step: The temperature is increased until the volatilized molecules are dissoci-
ated and produce an atomic vapor of the analyte. Atomization temperature is a property
specific to each element and recommended in the analytical procedure. Excessively high
temperatures cause decreased sensitivity and shorten the lifetime of the graphite tube.
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Interrupting the internal gas flow during atomization is desirable. This increases the resi-
dence time of the atomic vapor in the furnace, maximizing sensitivity and minimizing in-
terference. At the beginning of this step, the spectrometer “read” function is triggered to
begin the measurement of light absorption.
5. Clean-out step: After atomization, increase the temperature to burn out all remaining sam-
ple residue in the graphite tube.
6. Cool-down step: Allow the furnace to cool down to near-ambient temperature before in-
troducing the next sample. In some systems, this step is automatically presented and does
not need to be programmed.
9.3.5 MEASURING THE GRAPHITE FURNACE AA SIGNAL

In FAA work, a constant absorbance is observed, but in a GrAA the signal is transient. As atomization
begins, analyte atoms are formed, and the signal increases. The signal will continue to increase until the
rate of atom generation becomes less than the rate of atom diffusion out of the furnace. The falling atom
population results in a signal that decreases until all atoms are lost and the signal has fallen to zero. To
determine the analyte content of the sample, the resulting peak-shaped signal must be quantitated.
Modern instrumentation provides the capability of integrating absorbance during the entire at-
omization period, yielding a signal equal to the integrated peak area, which is the area under the peak
signal. The peak area represents a count of all atoms present in the sample aliquot, regardless of
whether the atoms were generated early or late in the atomization process. Integrated peak-area
measurements are independent of the atomization rate and are therefore much less subject to matrix
effects. The peak area is preferred for graphite furnace analysis.
9.3.6 INSTRUMENT CALIBRATION

1. Prepare standards for instrument calibration by dilution of the metal stock solutions.
Prepare standards fresh daily.
2. Prepare a blank and at least three standards in the appropriate concentration range (see
Table 9.1). Match the acid background similar to the sample. Add the same matrix modi-
fier (if required for sample analysis) to the standard solutions.
3. Inject a suitable portion of each standard solution in order of increasing concentration.
Analyze each standard solution in triplicate to verify method precision.
4. Construct an analytical curve by plotting absorbance of the standard solutions vs. concen-
tration (see Section 6.6). Alternatively, use electronic instrument calibration if the instru-
ment has this capability.

1. Measure and dispense a known volume of sample into the furnace. The analytical range of
the furnace analysis can be controlled by varying the sample volume.
For very low concentrations, the maximum sample volume can be used.
For higher concentrations, the sample volume can be reduced. Smaller sample volumes
can also be used when sample availability is limited.
Sample maximum volume is up to 100 µl when the graphite platform is not used, and
less than 50 µl when the platform is in place. A convenient sample volume for analy-
sis is 20 µl. The use of an autosampler is recommended because it provides excellent
reproducibility and superior results.
2. Subject the sample to a multistep temperature program (see Section 9.3.4). When the tem-
perature is increased to the point where sample atomization occurs, the atomic absorption
measurement is taken.
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TABLE 9.1
Detection Limits and Concentration Ranges for GrAAS
Wavelength Detection Limit Optimum Concentration

Element (nm) (µg/l) Range (µg/l)
Aluminum (Al) 300.3 3 20–200
Antimony (Sb) 217.6 3 20–300
Arsenic (As) 193.7 1 5–100
Barium (Ba) 553.6 2 10–200
Beryllium (Be) 234.9 0.2 1–30
Cadmium (Cd) 228.8 0.1 0.5–10
Chromium (Cr) 357.9 2 5–100
Cobalt (Co) 240.7 1 5–100
Copper (Cu) 324.7 1 5–100
Iron (Fe) 248.3 1 5–100
Lead (Pb) 283.3 1 5–100
Manganese (Mn) 279.5 0.2 1–30
Molybdenum (Mo) 313.3 1 3–60
Nickel (Ni) 232.0 1 5–100
Selenium (Se) 196.0 2 5–100
Silver (Ag) 328.1 0.2 1–25
Selenium (Se) 224.6 5 20–300
Note: For Pb determination, the most sensitive 217.0 wavelength is recommended for instruments with background
correction capabilities.
3. Repeat until reproducible results are obtained.

4. Compare the absorbance value to the calibration curve to determine the concentration of
the element of interest. Alternatively, read results directly if the instrument is equipped
with this capability.
5. If the absorbance (or concentration) of the most concentrated sample is greater than the
absorbance (or concentration) of the standard, dilute that sample and reanalyze. If very
large dilutions are required, another technique (e.g., ICP) may be more suitable for the
sample. If the sample is diluted with water, add acid and matrix modifier to restore the con-
centration of both to the original.
9.3.8 CALCULATION
See Section 8.2.7.
9.4 INTERFERENCE AND THE GRAPHITE FURNACE

Determinations by GrAA are subject to significant interference. At the beginning of GrAA work, in-
terference was accepted as an unavoidable part of the technique. Using today’s instrumentation with
new corrected methodologies makes the current graphite furnace technology a potential and excel-
lent tool in metals analysis. Interference is divided into two categories: spectral and nonspectral.
9.4.1 SPECTRAL INTERFERENCE

Spectral interference occurs when the measured light absorption is erroneously high due to absorp-
tion by a species other than the analyte element. This type of interference results from light absorp-
tion by molecules or by atoms other than those of the analyte element.
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9.4.1.1 Emission Interference

The intense light emitted by the hot graphite tube or platform, called black body radiation, blinds
the photomultiplier tube and interferes with readings during atomization. The maximum intensity
of this interference is in the near-infrared wavelength region. Elements determined at the UV wave-
length range — for example, zinc at 213.9 nm — are free from this type of disturbance. However,
chromium at 357.9 nm and calcium at 422.7 nm are greatly affected, and barium at 553.6 nm is es-
pecially vulnerable.
Black body radiation can be controlled by reducing the monochromator slit height. Instruments
usually have two sets of monochromator slits; the “low” (sometimes called “alternate”) slits are used
with the graphite furnace to eliminate the emission interference problem. Attention to furnace align-
ment and maintenance is still required. Cleanliness of the graphite furnace and sample compartment
windows must also be maintained to prevent light scattering. Atomization temperature should be not
higher than that required for efficient analyte atomization.
9.4.1.2 Background Absorption

Background absorption or molecular absorption may occur when components of the sample matrix
volatilize during atomization, resulting in broadband absorption (sometimes covering tens or hun-
dreds of nanometers).
Several background correction techniques are available commercially to compensate for this
type of interference, including sample treatment, furnace control procedures, and optical back-
ground controls.
9.4.1.2.1 Addition of Matrix Modifier or Matrix Modification

This technique helps to control matrix and analyte volatilities. It is desirable that the matrix be more
volatile than the analyte, so that during the pyrolysis step all matrix components from the sample are
volatilized and analyte atoms are not lost. The matrix modifier is selected to increase matrix volatil-
ity or decrease analyte volatility. For example, add ammonium nitrate (NH4NO3) to samples with a
high sodium chloride (NaCl) matrix according to the following reaction:
NaCl + NH4NO3 → NaNO3 + NH4Cl (9.1)
NaCl is a relatively nonvolatile compound, and requires pretreatment temperatures that would re-
sult in the loss of many analytes. By adding ammonium nitrate, however, the sample matrix is con-
verted into more volatile components that can be driven off with high efficiency at lower pyrolysis
temperatures. Decomposition temperatures are:
NaCl — 1400°C
NH4NO3 — 210°C
NaNO3 — 380°C
NH4Cl — 330°C
The other type of matrix modification is adding matrix modifier to make the analyte less
volatile. An example is the addition of nickel nitrate to selenium determination. Selenium is highly
volatile, but in the presence of nickel it can be heated to 900°C or more without loss. This process
allows the removal of the sample matrix, which otherwise could not be driven off without loss of
the selenium. A mixed modifier, such as palladium plus magnesium nitrate, can be used with vari-
ous elements with excellent results. Table 9.2 lists substances added to the sample to remove inter-
ference in the GrAA method.
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TABLE 9.2
Matrix Modifiers Added to Sample To Eliminate Interference, GrAAS Technique
Element Matrix Modifiers
Aluminum (Al) Mg(NO3)2
Antimony (Sb) Mg(NO3)2 Ni(NO3)2
Arsenic (As) Mg(NO3)2, Ni(NO3)2
Beryllium (Be) Mg(NO3)2, Al(NO3)2
Cadmium (Cd) Mg(NO3)2, NH4H2PO4, (NH4)2SO4, (NH4)2S2O8
Chromium (Cr) Mg(NO3)2
Cobalt (Co) Mg(NO3)2, NH4H2PO4, ascorbic acid
Copper(Cu) NH4NO3, ascorbic acid
Iron (Fe) NH4NO3
Lead (Pb) Mg(NO3)2, NH4NO3, NH4H2PO4, LaCl3, HNO3, H3PO4,
ascorbic acid, oxalic acid
Manganese (Mn) Mg(NO3)2, NH4NO3, ascorbic acid
Nickel (Ni) Mg(NO3)2, NH4H2PO4
Seleium (Se) Ni(NO3)2, AgNO3, Fe(NO3)3, (NH4)6MO7O24
Silver (Ag) (NH4)2HPO4, NH4H2PO4
Tin (Sn) Ni(NO3)2, NH4NO3, (NH4)2HPO4, Mg(NO3)22, ascorbic acid
9.4.1.2.2 Varying the Sample Volume

This technique is also an effective way to control background absorption. Larger sample volumes im-
prove the ability to detect low analyte concentrations. Smaller sample size reduces the mass of the
background-producing sample matrix and reduces with it background absorption.
9.4.1.2.3 Using Different Wavelengths

This method can also reduce background absorption.
9.4.1.2.4 Continuum Source Background Correction

This technique employs the use of a continuum source to measure the background contribution to the
total measured signal. Instrument electronics then automatically remove the unwanted background
contribution, and provide the corrected result.
9.4.1.2.5 Zeeman Effect Background Correction

This correction provides the best precision and accuracy for the elimination of background absorp-
tion. See Section 7.7.2.
9.4.2 NONSPECTRAL INTERFERENCE

Nonspectral interference results when diverse components in the sample matrix inhibit the formation
of free analyte atoms. Accurate compensation of this interference is more difficult than correcting
background absorption.
9.4.2.1 Standard Additions Method

In this method, a known amount of analyte is added to an aliquot of the sample. The absorbance val-
ues of the unspiked and spiked samples are calculated or measured and compared to the added ana-
lyte. For detailed information, see Section 7.7.1.
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1. Inject a measured volume of the sample into the furnace device.

2. Dry, char or ash, and atomize samples according to the preset program, as described in
Sections 9.3.3 and 9.3.4.
3. Record the instrument response in absorbance or concentration as appropriate.
4. Add a known concentration of the element of interest to a separate portion of the sample
so as not to change significantly the volume of the sample. Mix well and determine in-
strument response.
5. Add a known concentration, preferably twice as much as was used in the first addition (as
in step 4) to a separate sample portion. Mix well and determine the concentration.
6. Plot the absorbance, or the instrument response for the sample, and the two portions with
known additions on the vertical axis with the concentration of the element added on the
horizontal axis of linear graph paper.
7. Draw a straight line connecting the three points and extrapolate to zero absorbance. The
intercept of the horizontal axis is the concentration of the sample. The concentration axis
to the left of the origin should be a mirror image of the axis to the right.
Figure 9.2 illustrates a typical standard addition plot.
9.4.2.2 Graphite Tube Surface

A number of elements tend to form nonvolatile carbide by their interaction with the surface of the
graphite tube. The wall of the tube is porous, allowing the sample solution to soak into the structure
of the graphite tube during drying, and during atomization the atomic vapor interacts with the porous
surface of the graphite and forms analyte carbides. These actions decrease free atom populations. A
pyrolytically coated graphite tube offers a denser surface and prevents nonspectral interference.
Pyrolytic coating can also increase the useful lifetime of the graphite tube.
9.4.2.3 L’vov Platform

B.V. L’vov, a pioneer in GrAAS, developed the use a small platform made from a flat piece of solid
pyrolytic graphite, which is placed in the bottom of the graphite tube (Figure 9.2). The sample is
pipeted into a shallow depression on the platform. Because the platform is prepared from pyrolytic
graphite, this dense surface prevents the sample from soaking into the surface, as well as carbide for-
mation, and also tolerates the high acid content of the sample. The other benefit of the platform is
that the sample experiences the temperature of the platform, not the temperature of the tube wall.
Graphite
Front View Tube Side-On
View
Platform
Top View
FIGURE 9.2 L’vov platform.

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Because the platform is heated by radiation from the tube wall, temperature changes in the sample
on the platform — and therefore in the vapor within the tube — are delayed compared with the tube
wall. Instead of volatilizing the analyte as the temperature is changing, the appropriate conditions can
be attained to volatilize the analyte after the tube wall and the gas phase have reached a more stable
or steady-state condition.
9.4.2.4 Matrix Modification

Temperature is increased by adding a matrix modifier (see Section 9.4.1). This process delays the re-
lease of the analyte into the furnace, allowing additional time to establish a constant furnace temper-
ature before atomization. When recommended, a matrix modifier is always used to improve resist-
ance to nonspectral interference. The addition of a matrix modifier delays the atomization until a con-
stant furnace temperature is reached.
9.4.2.5 Maximum Power Atomization

The release of analyte atoms into the same furnace environment for all analyte forms is the prereq-
uisite for the elimination of nonspectral interference. Rapid heating, or maximum power atomiza-
tion, increases the temperature of the tube atmosphere more rapidly and the analyte is volatilized
into a hotter environment. By increasing the temperature of the furnace during atomization, the tube
wall and atmosphere are heated much faster than the platform, thus ensuring a stabilized tube at-
mosphere temperature during atomization. Some furnace systems employ an optical temperature
sensor, or the time for maximum power heating is programmed based on the desired final atomiza-
tion temperature.
9.4.2.6 Fast Electronics

In order to provide accurate analytical results, a graphite furnace AA system must be capable of ac-
curately quantitating the peak absorbance signal. One potential limitation is the speed of the instru-
ment’s electronics. Fast electronics provide accurate measurement of the rapidly changing signal.
9.4.2.7 Baseline Offset Correction (BOC)

One complication of peak-area measurement has been the exaggerated effect of baseline drift. Even
a slight baseline change becomes noticeable when it accumulates over several seconds. To eliminate
this potential problem, baseline offset correction was developed. BOC measures the baseline reading
immediately prior to atomization. Each reading during the peak-area integration is then automati-
cally corrected for baseline offset. This eliminates all drift effects and improves the accuracy of peak-
area measurement. It also maintains the correction for sample blanks implemented with the auto-
matic zero adjustment.
9.5 STABILIZED TEMPERATURE PLATFORM FURNACE (STPF)

The goals of an analytical technique should be able to control all interference and deliver accurate
measurements. In the stabilized temperature platform furnace (STPF) system, all previously dis-
cussed techniques for eliminating interferences are simultaneously applied, resulting in an interfer-
ence-free analysis. Every part of the system is crucial to the effectiveness of the system in providing
accurate results.
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The functions of each element comprising the STPF system are as follows:
High-quality pyrolytic graphite tubes provide an impervious, nonreactive surface.

L’vov platform delays atomization until stable temperature conditions are achieved.
Maximum power atomization hastens establishment of a stable atomization temperature and
enhances the temperature lag between heating of the tube wall (and atmosphere) and the
platform.
Internal gas stop maximizes residence time of atoms in the furnace.
Fast spectrometer electronics provide accurate measurement of the rapidly changing signal.
Peak area measurement quantitates all analyte atoms passing through the furnace independent
of the matrix-dependent analyte volatilization rate.
Baseline offset correction improves accuracy of peak-area measurement by compensating for
small changes in the baseline.
Matrix modification improves matrix removal during pretreatment.
Zeeman effect background correction corrects for high sample background, structured back-
ground absorption, and spectral interference.
9.6 QUALITY CONTROL REQUIREMENTS

See Chapter 14.
9.7 MAINTENANCE OF GRAPHITE ATOMIC

ABSORPTION SPECTROPHOTOMETER
See Table 9.3.
9.8 PERFORMANCE CHECK OF GRAPHITE ATOMIC

ABSORPTION SPECTROPHOTOMETER
The criteria of the performance check of the GrAAS is the same as for FAAS (see Section 8.6) with
the exception of the concentration of the sensitivity check standards. These performance check stan-
dards are listed in Table 9.4.
TABLE 9.3
Maintenance of GrAAS
Maintenance Activity Frequency

Check graphite tube D
Flush autosampler tubing D
Clean furnace housing and injector tip W
Note: D = daily; W = weekly; SA = semiannually; I = instrumentation

specialist; C = on contract.
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TABLE 9.4
Performance Check for GrAAS
Element Concentration of Sensitivity Check Standard (µg/l)

Aluminum (Al) 0.05
Antimony (Sb) 0.04
Arsenic (As) 0.04
Barium (Ba) 0.03
Cadmium (Cd) 0.003
Cobalt (Co) 0.03
Chromium (Cr) 0.007
Copper(Cu) 0.01
Iron (Fe) 0.01
Manganese (Mn) 0.005
Molybdenum (Mo) 0.025
Nickel (Ni) 0.04
Lead (Pb) at 283 nm 0.025
Lead (Pb) at 217 nm 0.016
Selenium (Se) 0.06
Silicon (Si) 0.14
Tin (Sn) at 286 nm 0.14
Tin (Sn) at 224.6 nm 0.08
Titanium (Ti) 0.21
Vanadium (V) 0.15
Zinc (Zn) 0.0007
Note: The sensitivity check data here pertain to the metal concentrations in milligrams per
liter in aqueous solution, which will give a reading of approximately 0.200 absorbance
units when 20 µl (microliters) are used.
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Cold-Vapor Atomic Absorption

10 Spectrometry

Because the atoms of most atomic absorption elements cannot exist in a free ground state at room
temperature, heat must be applied to break the bonds and release free atoms. The atoms are produced
by supplying enough heat energy to the sample to dissociate the compounds into free atoms.
Only one element, mercury (Hg), is an exception. Because free Hg atoms can exist at room tem-
perature, Hg can be measured by atomic absorption without a heated device. This process is called
the cold-vapor technique. In the cold-vapor technique, the Hg is reduced by the addition of a stan-
nous (Sn2+) compound, which is a strong reducing agent. The volatile-free Hg is taken from the re-
action vessel by bubbling air through the solution; Hg atoms go through the tubing to the absorption
cell, which is placed in the light path of the AA spectrometer. As the Hg atoms pass into the sampling
cell, measured absorbance rises, indicating the increasing concentration of Hg atoms in the light path.
The highest absorbance observed during the measurement is taken as the analytical signal. The pro-
cedure is based on the absorption of radiation at 253.7 nm by mercury vapor. The absorbance is
measured as a function of Hg concentration and recorded in the usual manner.
10.1.1 ADVANTAGES
One of the advantages of the cold-vapor technique is high sensitivity, which is achieved through a
100% sampling efficiency. Because all mercury contained in the sample is released for measurement,
increasing the sample volume means that more mercury atoms are available to be transported to the
sample cell and measured.
10.1.2 LIMITATIONS
The cold-vapor technique is limited to Hg determination, because no other element offers the possi-
bility of chemical reduction to a volatile-free atomic state at room temperature. In addition to inor-
ganic forms of Hg, organic mercurials may also be present. These organo-mercury compounds will
not respond to the cold-vapor technique unless they are first broken down and converted to mercuric
ions. Potassium permanganate (KMnO4) oxidizes many of these compounds, and the subsequent ad-
dition of potassium persulfate (K2S2O8) completely solves this problem.
10.1.3 DETECTION LIMIT

When using the cold-vapor technique and a 100-ml sample size, the detection limit for Hg is 0.0002
mg/l or 0.2 µg/l for liquid samples and 5 µg/g for solid samples.
143
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10.2 APPARATUS
When possible, dedicate glassware for use in Hg analysis. Avoid glassware previously exposed to a
high level of Hg, such as glassware used in chemical oxygen demand (COD), total Kjeldahl nitrogen
(TKN), and chloride (Cl) determination.
10.2.1 ATOMIC ABSORPTION SPECTROPHOTOMETER

Any AAS unit with an open sample presentation area in which to mount the absorption cell is suit-
able. Instrument settings recommended by the manufacturer should be followed. Instruments de-
signed specifically for the measurement of mercury using the cold-vapor technique are commercially
available and may be substituted for the AAS.
10.2.2 MERCURY HOLLOW CATHODE LAMP (HCL) OR ELECTRODELESS

DISCHARGE LAMP (EDL)
Both HCL and EDL lamps are discussed in Section 7.3.1.
10.2.3 RECORDER
Any multirange, variable-speed recorder that is compatible with the UV detection system is suitable.
10.2.4 ABSORPTION CELL

Typically, the absorption cell is a glass or plastic tube approximately 2.5 cm in diameter. An 11.4-
cm-long tube has been found to be satisfactory but a 15-cm-long tube is preferable. Grind the tube
ends perpendicular to the longitudinal axis and cement the quartz windows in place. Attach the gas
inlet and outlet ports (6.4-mm diameter) 1.3 cm from each end.
10.2.5 CELL SUPPORT

Strap the cell to the flat nitrous oxide burner head or on another suitable support and align it in the
light beam to provide maximum transmittance.
10.2.6 AIR PUMP

Any peristaltic pump capable of delivering 2 liters of air per minute can be used. (Some references
recommend 1 liter of air per minute.) Any other regulated compressed air system or air cylinder is
also satisfactory.
10.2.7 FLOWMETER
Flowmeters capable of measuring airflow of 2 l/min are recommended. (Some references accept
1 l/min.)
10.2.8 AERATION TUBING

Use a straight glass frit with coarse porosity. Tygon tubing is used for the passage of the mercury
vapor from the sample bottle to the absorption cell and back.
10.2.9 REACTION FLASK

The reaction flask is typically a 250-ml Erlenmeyer flask or 300-ml BOD bottle fitted with a rubber
stopper to hold the aeration tube.
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Cold-Vapor Atomic Absorption Spectrometry 145
10.2.10 DRYING TUBE

Typically, the drying tube is 150 mm × 18 mm in diameter and contains 20 g of magnesium per-
chlorate (Mg(ClO4)2). A small reading lamp with a 60-W bulb with a suitable shade may be substi-
tuted to prevent condensation of moisture inside the cell. The lamp is positioned to shine on the ab-
sorption cell, maintaining the air temperature in the cell at about 10°C above ambient temperature.
10.2.11 CONNECTING TUBING

Glass tubing is used to pass the Hg vapor from the reaction flask to the absorption cell and to inter-
connect all the other components. Clear vinyl plastic (tygon or equivalent) tubing may be substituted
for glass. The apparatus for Hg determination by the cold-vapor technique is shown in Figure 10.1.
10.3 PROCEDURE
10.3.1 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
All samples must be collected using a sampling plan that addresses the considerations discussed in
Chapter 14. Due to the extreme sensitivity of the analytical procedure and the omnipresence of mer-
cury, care must be taken to avoid extraneous contamination. The sampling devices and sample con-
tainers should be free of mercury and the sample should not be exposed to conditions in the labora-
tory that may result in contact with airborne mercury contamination. Plastic or glass containers are
suitable for sample collection. All containers must be prewashed with detergent, acid, and reagent
grade water, as discussed in Section 14.3.
10.3.1.1 Aqueous Samples

Aqueous samples must be acidified to a pH of less than 2 with HNO3. The maximum holding times
for these samples are 38 days in glass containers and 13 days in plastic containers.
FIGURE 10.1 Schematic arrangement of equipment for measurement of mercury by the cold-vapor atomic
absorption technique.
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10.3.1.2 Nonaqueous Samples

Nonaqueous samples should be refrigerated, when possible, and analyzed as soon as possible.
10.3.1.3 Solid or Semisolid Samples

These samples may be analyzed directly and their moisture content determined separately.
Determination of moisture content of a sample is described in Appendix I. Analysis of dry samples
is more convenient. Moisture can be removed in a drying oven at a temperature of 60°C; no mercury
losses have been observed when using this drying step. The dry sample must be pulverized and thor-
oughly mixed before the aliquot is weighed for analysis.
10.3.2 REAGENTS
All chemicals and the reagent-grade water should be mercury free!
10.3.2.1 Aqua Regia

Prepare immediately before use by carefully adding three volumes of HCl concentrate to one volume
of HNO3 concentrate.
10.3.2.2 Sulfuric Acid (H2SO4) Concentrate
10.3.2.3 H2SO4, 0.5N

Dilute 14 ml of concentrated H2SO4 to 1 liter.
10.3.2.4 Nitric Acid (HNO3) Concentrate
10.3.2.5 Stannous Ion (Sn2+) Solution

Use either stannous chloride or stannous sulfate to prepare this solution containing about 7 g Sn2+
per 100 ml. Dissolve 10 g of SnCl2 in analyte-free water containing 20 ml of HCl concentrate and
dilute to 100 ml, or dissolve 11 g of SnSO4 in analyte-free water containing 7 ml of H2SO4 concen-
trate and dilute to 100 ml. If a suspension forms, stir the reagent continuously during use. Both so-
lutions decompose with aging; therefore, prepare fresh solutions daily. A reagent volume of 100 ml
is sufficient for 20 samples; adjust the volumes prepared to accommodate the number of samples
processed.
10.3.2.6 Sodium Chloride–Hydroxylamine Sulfate Solution

Dissolve 12 g of NaCl and 12 g (NH2OH)2.H2SO4 in mercury-free, reagent-grade water and dilute to
1 liter A 10% hydroxylamine hydrochloride may be used in place of hydroxylamine sulfate.
10.3.2.7 Potassium Permanganate 5% Solution

Dissolve 50 g of KMnO4 in reagent-grade water and dilute to 1 liter. Store the solution in a glass-
stoppered, amber-colored glass bottle.
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10.3.2.8 Potassium Permanganate 0.1N Solution

Dissolve 3.2 g of KMnO4 in about 100 ml of reagent-grade water and dilute to 1000 ml. Allow the
solution to stand in the dark for a few days and then filter through a fine-porosity sintered glass cru-
cible. Do not use filter paper! Store the solution in a glass-stoppered, amber-colored glass bottle.
10.3.2.9 Potassium Persulfate 5% Solution

Dissolve 50 g of K2S2O8 in reagent-grade water and dilute to 1 liter.
10.3.2.10 Stock Mercury Solution

Dissolve 0.1354 g of HgCl2 in 75 ml reagent-grade water. Add 10 ml of HNO3 concentrate and ad-
just the volume to 100 ml.
10.3.2.10.1 Working Standard Mercury Solution, 1 ml = 0.1 µg Hg

Dilute from the stock mercury solution in two steps:
1. Dilute 1 ml of stock solution to 100 ml: 1 ml = 0.01 mg Hg = 10 µg Hg.

2. Dilute 1 ml of solution in number 1 to 100 ml: 1 ml = 0.0001 mg Hg = 0.1 µg Hg.
This working standard and the dilutions from the stock solution should be prepared fresh daily. The
acidity of the working standard should be maintained at 0.15% HNO3. This acid should be added to
the flask before the aliquot is added.
10.3.3 INSTRUMENT OPERATION

Because of differences among makes and models of atomic absorption spectrophotometers, it is not
possible to formulate instructions applicable to every instrument. See the manufacturer’s operation
manual. In general, proceed according to the following steps:
1. Install the hollow cathode lamp (HCL) for Hg in the instrument.

2. Set the slit width according to the manufacturer’s suggestion.
3. Turn on the instrument.
4. Apply the current suggested by the manufacturer to the HCL and let the instrument warm
up until the energy source stabilizes (generally 10–20 min).
5. Readjust the current as necessary after warm-up.
6. Set the wavelength to 253.7 nm.
7. Install the absorption cell and align it in the light path to provide maximum transmission.
8. Connect the associated equipment to the absorption cell with glass or vinyl plastic tubing
as indicated in Figure 10.1.
9. Turn on the air and adjust the flow rate to 2 l/min. Allow the air to flow continuously.
1. Set out correct number and type of reaction flasks (Section 10.2.9). Start with a blank and
follow with standards (calibration standards, continuing calibration standard, and calibra-
tion verification standard, or quality control sample). For detailed discussion of these stan-
dards, see Section 13.6.2.
2. Transfer 0, 0.5, 1.0, 2.0, 5.0, and 10.0 ml of aliquot of the working standard solution con-
taining 0.1 µg Hg per ml (Section 10.3.2) to the bottles marked as calibration standards.
3. Add enough analyte-free water to each bottle to make a total volume of 100 ml.
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4. Add 5 ml of H2SO4 concentrate followed by 2.5 ml of HNO3 concentrate to each flask.

5. Add 15 ml of potassium permanganate solution (Section 10.3.2) to each bottle and allow
to stand for at least 15 min.
6. Add 8 ml of potassium persulfate solution (Section 10.3.2) to each bottle and heat for 2 h
in a water bath maintained at 95°C. Cool to room temperature.
7. Treating each flask individually, add 6 ml of sodium chloride–hydroxylamine sulfate
(Section 10.3.2) solution (or more if necessary) to reduce the excess permanganate.
8. When the solution has been decolorized, wait 30 sec, add 5 ml of Sn2+ solution (Section
10.3.2), and immediately attach the bottle to the aeration apparatus. At this point the sam-
ple is allowed to stand quietly without manual agitation. The circulating pump (Section
10.2.6), which has previously been adjusted to a rate of 2 l/min, is allowed to run contin-
uously. As the Hg is volatilized and carried into the absorption cell, absorbance will in-
crease and reach a maximum within 30 sec.
9. As soon as the recorder returns approximately to the baseline, remove the stopper holding
the frit from the reaction flask and replace it in a flask containing reagent-grade water.
10. Flush system for a few seconds and run the next standard in the same manner.
11. Close the bypass valve, remove the stopper and frit from the BOD bottle, and continue
aeration.
12. Construct a calibration curve by plotting the absorbances of the standards vs. the micro-
gram of mercury. Preparation and checking of the calibration curve are discussed in
Section 6.6.

10.3.5.1 Liquid Samples
The cold-vapor method is applicable to liquid samples, such as ground waters, drinking waters,
aqueous wastes, and mobility procedure extracts.
1. Transfer a 100-ml sample or portion diluted to 100 ml, containing not more than 1.0 µg of
Hg, to a 300-ml BOD bottle (Section 10.2.9).
2. Add 5 ml of H2SO4 concentrate and 2.5 ml of HNO3 concentrate, mixing after each
addition.
3. Add 15 ml of potassium permanganate solution (Section 10.3.2.7) to each sample flask.
Sewage samples may require additional KMnO4 solution; add until the purple color per-
sists for at least 15 min.
4. Add 8 ml of potassium persulfate solution (Section 10.3.2) to each bottle and heat for 2 h
in a water bath maintained at 95°C.
5. Cool and add 6 ml of sodium chloride–hydroxylamine sulfate solution (Section 10.3.2.6)
to reduce the excess permanganate.
6. Follow the procedure described in Section 10.3.4, steps 8 through 10.
Note: Seawaters, brines, and effluents high in chloride require up to 25 ml of additional potassium
permanganate solution. During the oxidation step, chlorides are converted to free chlorine, which ab-
sorbs at 253 nm. Remove the free chlorine before the Hg is reduced and swept into the cell by using
an excess (25 ml) of hydroxylamine sulfate (Section 10.3.2.6) reagent. In addition, the dead air space
in the BOD bottle must be purged before adding the Sn2+ solution (Section 10.3.2.5). All samples that
suffer from matrix interference should be analyzed by the standard addition method (Section
7.7.1.1.1).
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10.3.5.2 Solids and Semisolids

This method is applied to determine the total mercury content in soils, sediments, bottom deposits,
and sludge-type materials. All samples must be subjected to an appropriate dissolution step prior to
analysis.
1. Weigh three 0.2-g portions of untreated sample and place them in the bottom of a BOD
bottle.
2. Add 5 ml of analyte-free, reagent-grade water.
3. Add 5 ml of aqua regia (Section 10.3.2.1).
4. Heat for 2 min in a water bath at 95°C.
5. Cool and then add 50 ml of analyte-free, reagent-grade water and 15 ml potassium per-
manganate solution (Section 10.3.2.7).
6. Mix thoroughly and place in a water bath for 30 min at 95°C.
7. Cool and add 6 ml of sodium chloride–hydroxylamine sulfate (Section 10.3.2.6) to reduce
the excess potassium permanganate. Add this material under a hood, as chlorine (Cl2)
could evolve.
8. Add 55 ml of analyte-free water.
9. Treating each bottle individually, add 5 ml of stannous sulfate reagent (Section 10.3.2.5)
and immediately attach the bottle to the aeration apparatus.
Note: An alternate digestion procedure employing an autoclave may also be used. In this case use the
following steps:
1. Weigh three 0.2-g portions of untreated sample and place them in the bottom of a BOD
bottle.
2. Add 5 ml of analyte-free, reagent-grade water.
3. Add 5 ml of H2SO4 concentrate and 2 ml of HNO3 concentrate to the 0.2-g sample.
4. Add 5 ml of saturated potassium permanganate solution.
5. Cover the bottle with a piece of aluminum foil.
6. Autoclave the samples at 121°C and 15 lb for 15 min.
7. Cool and dilute to a volume of 100 ml with reagent-grade water.
8. Add 6 ml of sodium chloride–hydroxylamine sulfate solution (Section 10.3.2.6) to reduce
the excess permanganate.
10.4 INTERFERENCE
10.4.1 SULFIDES
Sulfide interference is eliminated by the addition of KMnO4. Concentrations as high as 20 mg/l of
sulfide as sodium sulfide do not interfere with the recovery of added inorganic mercury from dis-
tilled water.
10.4.2 COPPER
Copper has also been reported to interfere; however, copper concentrations as high as 10 mg/l have
no effect on the recovery of Hg from spiked samples.
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10.4.3 SEAWATERS, BRINES, AND INDUSTRIAL EFFLUENTS HIGH IN CHLORIDES

These materials require additional permanganate (up to 25 ml). During the oxidation step, the chlo-
rides are converted to free chlorine, which also absorbs radiation at 253.7 nm. Care must be taken to
ensure that free chlorine is absent before the mercury is reduced and swept into the cell. This may be
accomplished by using an excess of hydroxylamine sulfate reagent (Section 10.3.2.6) (25 ml). In ad-
dition, the dead air space in the BOD bottle must be purged before adding stannous sulfate (Section
10.3.2.5). Both inorganic and organic mercury spikes have been recovered from seawater by using
this technique.
10.4.4 CERTAIN VOLATILE ORGANIC MATERIALS

These materials also absorb radiation at 253.7 nm, which may cause interference. A preliminary
run without reagents should determine if this type of interference is present. In order to remove
any volatile materials, the dead air space in the BOD bottle should be purged before adding the
stannous reagent.

1. All quality control data should be maintained and available for easy reference or inspec-
tion.
2. Calibration curves must be composed of at least one blank and three standards. A calibra-
tion curve should be made for every hour of continuous sample analysis.
3. Dilute samples if they are more concentrated than the highest standard or if they fall on the
plateau of a calibration curve.
4. Employ a minimum of one blank per sample batch to determine if contamination or mem-
ory effects are occurring.
5. Verify calibration with an independently prepared calibration verification standard (CVS)
every 15 samples.
6. Run one spiked duplicate sample for every ten samples. A duplicate sample must be
brought through the entire sample preparation and analytical process.
7. The standard addition method (Section 7.7.1) should be used in all extraction procedure
toxicity (EPTOX) tests, analyses submitted as part of a de-listing petition, and analysis of
a new sample matrix.
Detailed quality control requirements are discussed in Chapter 13.
10.6 CALCULATIONS AND REPORTING

Calculate metal concentrations from the calibration curve. All dilution and concentration factors
must be taken into account. Report the results for liquid samples as micrograms or nanograms per
liter; for solid samples, use micrograms or nanograms per gram. All results must be appropriately
qualified for dry weight (see Appendix I).
Report Hg concentration for liquid samples as milligrams or micrograms per liter; for solid
samples, report as micrograms per gram on the dry-weight basis. (See Appendix I for calcula-
tion.) Report Hg concentrations as follows: below 0.1 µg/g; between 0.1 and 1.0 µg/g to the near-
est 0.01 µg; between 1.0 and 10 µg/g to the nearest 0.1 µg; and above 10 µg/g to the nearest mi-
crogram.
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10.7 SAFETY
Because Hg vapor is toxic, precautions must be taken to avoid inhalation. Therefore, a bypass has
been included in the system either to vent the mercury vapor into an exhaust hood or to pass the vapor
through some absorbing medium, such as equal volumes of 0.1N KMnO4 and 10% H2SO4, or 0.25%
iodine in a 3% potassium iodide (KI) solution. A specially treated charcoal that will absorb mercury
vapor is also available from Barnebey and Cheney (East 8th Ave. and North Cassidy St., Columbus,
OH 43219; Cat. No. 580–13 or 580–22).
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Hydride-Generation Atomic
11 Absorption Technique
11.1 PRINCIPLE
Hydride-generation sampling systems for atomic absorption bear some resemblance to cold-vapor
mercury systems. Samples are reacted in an external vessel with a reducing agent, usually sodium
borohydride. Gaseous reaction products are then carried to a sampling cell in the light path of the AA
spectrometer. Unlike the mercury technique, the gaseous reaction products are not free-analyte atoms
but volatile hydrides. These molecular species are not capable of causing atomic absorption. To dis-
sociate the hydride gas into free atoms, the sample cell must be heated.
In some hydride systems, the absorption cell is mounted over the burner head of the AA spec-
trometer, and the cell is heated by an air–acetylene flame. In other systems, the cell is heated electri-
cally. In either case, the hydride gas is dissociated in the heated cell into free atoms, and the atomic
absorption rises and falls as the atoms are created and then escape from the absorption cell. The max-
imum absorption reading, or peak height, is taken as the analytical signal. Recommended wave-
lengths are 193.7 nm for As and 196.0 nm for Se.
11.1.1 ADVANTAGE
The advantage of the technique is the easily achievable detection limits below micrograms per liter.
11.1.2 DISADVANTAGE
The disadvantage of the technique is that its results depend heavily on a variety of parameters, in-
cluding the valence state of the analyte, reaction time, gas pressures, concentration, and cell temper-
ature. Therefore, the success of the hydride generation technique will vary with the care taken by the
operator in attending to the required detail. The formation of analyte hydrides is also suppressed by
a number of common matrix components, leaving the technique subject to chemical interference.
11.2 APPLICATION
The method is applicable to the determination of arsenic (As) and selenium (Se) via conversion to
their hydrides with sodium borohydride reagent and aspiration into an atomic absorption atomizer.
Arsenous acid and selenous acid, the As(III) and Se(IV) oxidation states of As and Se, respec-
tively, are instantaneously converted by sodium borohydride reagent in acid solution to their volatile
hydrides. The hydrides are purged continuously by argon or nitrogen into an appropriate atomizer of
an AA spectrometer and converted to the gas-phase atoms. The sodium-borohydride reducing agent,
by rapid generation of the elemental hydrides in an appropriate reaction cell, minimizes dilution of
the hydrides by the carrier gas and provides rapid, sensitive determinations of As and Se.
153
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Caution: As and Se and their hydrides are toxic. Handle with care!
At room temperature and solution pH values of 1 or less, arsenic acid, the As(V) oxidation state
of As, is reduced relatively slowly by sodium borohydride to As(III), which is then instantaneously
converted to arsine. The arsine atomic-absorption peaks are commonly lower for As(V) than for
As(III). Determination of total As requires that all inorganic arsenic compounds be in the As(III)
state. Organic and inorganic forms of As are first oxidized to As(V) by acid digestion. The As(V) is
then reduced to As(III) with sodium or potassium iodide before reaction with sodium borohydride.
Selenic acid, the Se(VI) oxidation state of Se, is not measurably reduced by sodium borohydride.
To determine total Se, first reduce the Se(VI) formed during the acid digestion procedure to Se(IV),
being careful to prevent reoxidation by chlorine. Reduction efficiency depends on temperature re-
duction time and HCl concentration. For 4N HCl concentration, heat 1 h at 100°C; for 6N HCl, boil-
ing for 10 min is sufficient. Recommended wavelengths are 193.7 nm for As and 196.0 nm for Se.
11.2.1 DETECTION LIMIT AND CONCENTRATION RANGE

For both As and Se, the method detection limit is 0.002 mg/l and the optimum concentration range
is 0.002 to 0.02 mg/l.
11.3 APPARATUSES AND MATERIALS

11.3.1 ATOMIC ABSORPTION SPECTROMETER
Use an AA spectrometer equipped with gas-flow meters for argon (or nitrogen) and hydrogen.
11.3.2 ARSENIC AND SELENIUM HOLLOW CATHODE LAMP

OR ELECTRODELESS DISCHARGE LAMP
Use an As and Se hollow cathode lamp (HCL) or electrodeless discharge lamp (EDL) with power sup-
ply.
11.3.3 BACKGROUND CORRECTION AT MEASUREMENT OF WAVELENGTH

11.3.4 STRIP-CHART RECORDER
A high-quality 10-mV recorder with high sensitivity and fast response time is required.
11.3.5 ATOMIZER
Certain atomic absorption atomizers and hydride reaction cells are available commercially for use
with the sodium borohydride reagent. Three types of atomic absorption atomizers are commonly
used in the measurement of As and Se:
• Boling-type burner: For argon (or nitrogen) air-entrained hydrogen flame

• Cylindrical quartz cell externally heated: 10 to 20 cm long, electrically heated by external
nichrome wire to 800–900°C.
• Cylindrical quartz cell with internal fuel, oxygen-hydrogen or air-hydrogen flame: The
sensitivity of quartz cells deteriorates over several months of use. Sensitivity may be re-
stored by treatment with 40% HF.
Caution: HF is extremely corrosive. Avoid all contact with skin. Handle with care!
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Hydride-Generation Atomic Absorption Technique 155
11.3.6 REACTION CELL FOR PRODUCING AS AND SE HYDRIDE

A commercially available system is acceptable. (See Figure 11.1.)
11.3.7 EYE DROPPER OR SYRINGE

The eye dropper or syringe should be capable of delivering 0.5 to 3.0 ml of sodium borohydride
reagent (Section 11.3.9.1).
11.3.8 VENT
Place a vent about 15 to 30 cm above the burner to remove fumes and vapors from the flame. This
precaution protects laboratory personnel from toxic vapors, protects the instrument from corrosive
vapors, and prevents flame stability from being affected by room drafts.
Commercially available continuous hydride generator units make the operation simpler than the
manual method.
11.3.9 REAGENTS
11.3.9.1 Sodium Borohydride Reagent
Dissolve 8 g of NaBH4 in 200 ml of 0.1N NaOH. Prepare fresh daily.
11.3.9.2 Sodium Hydroxide (NaOH), 0.1N
Dissolve 4 g of NaOH and dilute to 1000 ml.
11.3.9.3 Sodium Iodide Prereductant
Dissolve 50 g of NaI in 500 ml of reagent water. Prepare fresh daily.
FIGURE 11.1 Manual reaction cell for producing As and Se hydrides.

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11.3.9.4 Sulfuric Acid (H2SO4), 18N

Very carefully make a 50% dilution (1:1) of H2SO4 concentrate (H2SO4 concentrate is 36N).
11.3.9.5 Sulfuric Acid (H2SO4), 2.5N

Cautiously add 35 ml of H2SO4 concentrate to about 400 ml of reagent-grade water, let cool, and ad-
just volume to 500 ml.
11.3.9.6 Potassium Persulfate, 5%

Dissolve 25 g of K2S2O8 in reagent-grade water and dilute to 500 ml. Store in glass bottle and refrig-
erate. Prepare fresh weekly.
11.3.9.7 Nitric Acid (HNO3) Concentrate

11.3.9.8 Hydrochloric Acid (HCl) Concentrate
11.3.9.9 Perchloric Acid (HClO4) Concentrate
11.3.9.10 As(III) Solutions
11.3.9.10.1 Stock As(III) Solution, 1 ml = 1.0 mg As(III)

Either procure a certified aqueous standard from a supplier or dissolve 1.32 g of arsenic trioxide
(As2O3) in reagent-grade water containing 4 g of NaOH, and dilute to 1000 ml.
11.3.9.10.2 Intermediate As(III) Solution, 1 ml = 10 mg As(III)
Dilute 10 ml of stock As(III) solution (Section 11.3.9.10.1) to 1000 ml with reagent-grade water con-
taining the same concentration of acid used for sample preservation (2–5 ml of HNO3 concentrate).
11.3.9.10.3 Standard As(III) Solution, 1 ml = 0.100 mg As(III)
Dilute 10 ml of intermediate As(III) solution (Section 11.3.9.10.2) to 1000 ml with reagent-grade
water containing acid at the same concentration as used for sample preservation (2 to 5 ml HNO3 con-
centrate). Prepare the solution fresh daily.
11.3.9.11 As(V) Solutions

11.3.9.11.1 Stock As(V) Solution, 1 ml = 1.00 mg As(V)
Dissolve 1.534 g of arsenic pentoxide (As2O5) in reagent-grade water containing 4 g of NaOH. Dilute
to 1 liter.
11.3.9.11.2 Intermediate As(V) Solution, 1 ml = 10.0 mg As(V)
Prepare as As(III) intermediate standard (Section 11.3.9.10.2), but use stock As(V) solution (Section
11.3.9.11.1).
11.3.9.11.3 Standard As(V) Solution, 1 ml = 0.110 mg As(V)
Prepare as for As(III) above (Section 11.3.9.10.3), but use intermediate As(V) solution (Section
11.3.9.11.2).
11.3.9.12 Organic As Solutions

11.3.9.12.1 Stock Organic As Solution, 1 ml = 1 mg Org As
Dissolve 1.842 g dimethyl-arsinic (cacodylic acid, (CH3)2AsOOH) in reagent-grade water containing
4 g of NaOH. Dilute to 1 liter.
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11.3.9.12.2 Intermediate Organic As Solution, 1 ml = 10.0 mg Org As

Prepare as for As(III) (Section 11.3.9.10.2) but use stock organic As solution.
11.3.9.12.3 Standard Organic As Solution, 1 ml = 0.100 mg Org As
Prepare as for As(III) above (Section 11.3.9.10.3), but use intermediate organic As solution (Section
11.3.9.12.2).
11.3.9.13 Se(IV) Solutions

11.3.9.13.1 Stock Se(IV) Solution, 1 ml = 1.00 mg Se(IV)
Use a commercially available 1000 mg/l Se standard solution or prepare by dissolving 2.190 g of
sodium selenite (Na2SeO3) in reagent-grade water containing 10 ml of HCl concentrate and dilute to
1000 ml. (Alternatively, you can use 0.3453 g of selenious acid (H2SeO3) and dilute to 200 ml.)
11.3.9.13.2 Intermediate Se(IV) Solution, 1 ml = 10.0 mg Se(IV)
Dilute 10 ml of stock Se(IV) solution to 1000 ml with reagent-grade water containing 10 ml of HCl
concentrate.
11.3.9.13.3 Standard Se(IV) Solution, 1 ml 0.100 mg As(IV)
Dilute 10 ml of intermediate Se(IV) solution to 1000 ml with water containing the same acid con-
centration used for sample preservation (2–5 ml of HNO3 concentrate). Prepare the solution daily.
11.3.9.14 Se(VI) Solutions

11.3.9.14.1 Stock Se(VI) Solution, 1 ml = 1.00 mg As(IV)
Dissolve 2.393 g of sodium selenate (Na2SeO4) in reagent-grade water containing 10 ml of HNO3
concentrate and dilute to 1000 ml.
11.3.9.14.2 Intermediate Se(VI) Solution, 1 ml = 10 mg As(VI)
Dilute 10 ml of stock Se(VI) (Section 11.3.9.14.1) to 1000 ml with reagent-grade water.
11.3.9.14.3 Standard Se(VI) Solution, 1 ml = 0.100 mg As(VI)
Prepare as Se(IV) standard solution (Section 11.3.9.13.3), but use intermediate Se(VI) solution
(Section 11.3.9.14.2).
11.4 INTERFERENCES
Interference is minimized because the As and Se hydrides are removed from the solution con-
taining interfering substances. Interferences depend on system design. Certain waters and waste-
waters contain interferences in sufficient concentration to suppress absorption responses. If aver-
age analytical recoveries of the sample are less than 90%, use an alternative analytical procedure.
11.4.1 POSSIBLE INTERFERENCES
• Low concentrations of noble gases (100 mg/l)
• Concentrations of Cu, Pb, and Ni at or greater than 1 mg/l
• Concentrations between 0.1 and 1 mg/l of hydride-forming elements such as Bi, Sb, Sn,
and Te
• Interference by transition metals that depends strongly on HCl concentration; 4N HCl or
6N HCl (see Section 11.2) is recommended
• Reduced nitrogen oxide resulting from HNO3 digestion, suppressing instrumental response
• Large concentrations of iodide interfering with Se determination by reducing Se to its el-
emental form
• Chlorine gas produced in the reduction of Se(VI) to Se(IV) preventing generation of the
hydride within a few hours of the reduction steps
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11.5 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

• All samples must have been collected using a sampling plan.
• All sample containers must be prewashed with detergents, acids, and reagent-grade water.
Glass and plastic containers are both suitable as discussed in Section 14.3.
• Aqueous samples must be acidified to a pH of less than 2 with HNO3 (see Section 14.4).
• Nonaqueous samples should be refrigerated, when possible, and analyzed as soon as
possible.
11.6 PREPARATION OF SAMPLES AND STANDARDS FOR TOTAL

ARSENIC AND SELENIUM
1. Add 50 ml of sample or standard to a 200-ml Berzelius beaker or 300-ml beaker.
2. Add 1 ml of 2.5N H2SO4 and 5 ml of 5% K2S2O8. Boil gently on a preheated hot plate for
approximately 30 to 40 min or until a final volume of 10 ml is reached. Do not let sam-
ple evaporate to dryness. Alternatively, heat in an autoclave at 121°C for 1 h in capped
containers.
3. After manual digestion, dilute to 50 ml for arsenic measurement and 30 ml for selenium
measurement.
11.7 PROCEDURE
11.7.1 APPARATUS SETUP
See Figure 11.1 or follow manufacturer’s instructions.
1. Connect inlet of reaction cell with auxiliary, purging gas controlled by flow meter.
2. If a dryimg cell between the reaction cell and atomizer is necessary, use only anhydrous
CaCl2 (but not CaSO4 because it may retain SeH2).
3. Optimize operating parameters. Aspirate diluted aqueous solutions of As and Se directly into
the flame to facilitate atomizer alignment. Align quartz atomizers for maximum absorbance.
4. Aspirate a blank until memory effects are removed.
5. Establish purging gas flow, concentration and rate of addition of sodium borohydride
reagent, solution volume, and stirring rate for optimum instrument response for the species
analyzed.
6. If a quartz atomizer is used, optimize cell temperature.
7. If sodium borohydride reagent is added too quickly, rapid evolution hydrogen will unbal-
ance the system.
8. If the volume to be analyzed is too large, the absorption signal will be decreased.
11.7.2 INSTRUMENT CALIBRATION STANDARDS

1. Transfer 0, 1, 2, 5, 10, 15, and 20 ml of standard solution of As(III) (Section 11.3.9.10.3)
or Se(IV) (Section 11.3.9.13.3) into 100-ml volumetric flasks.
2. Bring to volume with reagent-grade water containing the same acid concentration used for
sample preservation (commonly 2–5 ml/l of HNO3 concentrate).
These steps yield blank and standard solutions of 0, 1, 2, 5, 10, 15, and 20 µg/l of As or Se. Prepare
fresh daily.
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11.7.3 DETERMINATION OF AS AND SE WITH SODIUM BOROHYDRIDE

11.7.3.1 Determination of As
1. Measure 50 ml of standard or sample in a 200-ml Berzelius beaker or 300-ml beaker.
2. Add 5 ml of HCl concentrate and mix.
3. Add 5 ml of NaI solution (Section 11.3.9.3), mix, and wait at least 30 min.
4. Attach one Berzelius beaker at a time to the rubber stopper containing the gas disper-
sion tube for the purging gas, the sodium borohydride reagent inlet, and the outlet to
the atomizer.
5. Turn on the strip-chart recorder and wait until the baseline is established by purging gas
and expelling all air from the reaction cell.
6. Add 0.5 ml of sodium borohydride reagent (Section 11.3.9.1).
7. After the instrument absorbance has reached a maximum and returned to the baseline, re-
move beaker, rinse dispersion tube with water, and proceed to the next sample or standard.
8. Check for presence of chemical interferences by treating a digested sample with 10 mg/l
As(III) or As(V) as appropriate. Average recoveries should be no less than 90%.
11.7.3.2 Determination of Se
1. Measure 30 ml of standard or sample into a 200-ml Berzelius beaker or 300-ml beaker.
2. Add 15 ml of HCl concentrate and mix.
3. Heat for a predetermined period at 90 to 100°C. Alternatively, autoclave at 121°C in
capped containers for 60 min or heat for a predetermined period in open test tubes at 90 to
100°C in hot water bath or an aluminum block digester. Effective heat exposure for con-
verting Se(VI) to Se(IV) ranges from 5 to 60 min when open beakers or test tubes are used.
Check effectiveness of selected heating by demonstrating equal instrument responses for
calibration curves prepared either from Se(IV) or Se(VI) solutions. Do not digest these so-
lutions used for this check!
4. Attach Berzelius beakers one at a time to the purge apparatus, turn on the strip-chart
recorder, and wait until the baseline is established.
5. Add 0.5 ml of sodium borohydride reagent (Section 11.3.9.1).
6. After the instrument absorbance has reached a maximum and returned to the baseline, re-
move beaker, rinse dispersion tube, and proceed to the next sample or standard.
7. Check for the presence of chemical interferences by treating a digested sample with 10
mg/l Se(IV). Average recoveries should be not less than 90%.
11.7.4 CALCULATIONS
Construct a calibration curve by plotting peak heights vs. concentration of standards, and read con-
centration from curve. On instruments so equipped, read concentration directly after calibration. If
sample was diluted or concentrated before digestion, apply the appropriate factor.

See Chapter 13.
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Inductively Coupled Plasma

12 Atomic Emission Spectroscopy
12.1 ATOMIC EMISSION SPECTROSCOPY (AES)

In AES, the sample is subjected to temperatures high enough to cause not only dissociation into
atoms, but also significant amounts of collisional excitation (and ionization) of the sample atoms.
Once the atoms and ions are in their excitation states, they can decay to lower states through thermal
or radioactive (emission) energy transition. (See discussion of emission in Section 5.4.) In AES, the
intensity of the light emitted is measured at specific wavelengths and used to determine the concen-
trations of the elements of interest.
Thermal excitation sources can populate a large number of different energy levels for several dif-
ferent elements at the same time. Consequently, all excited atoms and ions can emit characteristic ra-
diation at nearly the same time. In general, three types of thermal sources are used in analytical
atomic spectrometry to dissociate sample molecules into free atoms: flames, furnaces, and electrical
discharges. The first two types are hot enough to dissociate most types of molecules into free atoms.
Electrical discharges, the third type, are also called plasmas.
12.1.1 PLASMAS
Plasma is a state of matter usually consisting of highly ionized gas that contains an appreciable frac-
tion of equal numbers of ions and electrons in addition to neutral atoms and molecules. Plasmas con-
duct electricity and are affected by magnetic fields. The plasma source has a high degree of stability
to overcome interference effects. Plasma is capable of exciting several elements that are not excited
by flames and has increased sensitivity to flame AES. The low detection limits, freedom from inter-
ferences, and long-line working ranges prove that it is a superior technique for AES. For more detail
about plasmas, see Appendix J.
The electrical plasmas used in AES work are highly energetic ionized gases and are usually pro-
duced in inert gases. The plasma source for analytical AES is argon-supported inductively coupled
plasma (ICP).
12.1.2 SHORT HISTORY OF AES

In the 1860s, Kirchhoff and Bunsen developed methods based on emission spectroscopy that led to
the discovery of four elements: cesium (Cs), rubidium (Rb), titanium (Ti), and indium (In). At this
time, the emitted lines were used in qualitative analytical work.
In the mid-twentieth century, quantitative emission spectroscopy was the tool used to determine
trace concentrations for a wide range of elements, but sample preparation techniques were very dif-
ficult and time consuming.
The atomic spectra emitted from flames had the advantage of being simpler and easier. This tech-
nique, called flame emission spectrometry (also known as flame photometry) is used to determine
161
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alkali metals and other easily excitable elements. Swedish agronomist Lundegardth is credited with
initiating the modern era of flame photometry in the late 1920s. This technique is commonly used in
clinical laboratories for determining sodium and potassium levels in biological materials.
In the 1960s and 1970s, flame atomic absorption (FAA) was the preferred technique for the deter-
mination of trace metals. FAA offers high precision and moderate detection limits. Electrothermal at-
omization, or graphite furnace atomic absorption spectrophotometry (GrAAS), on the other hand, of-
fers high sensitivity and lower detection limits, but poorer precision and a higher level of matrix inter-
ferences. However, most of these interferences have been reduced or eliminated (see Section 9.4). Both
FAA and GrAAS techniques are widely used today and provide excellent means of trace element analy-
sis. However, most atomic absorption instruments are limited in that they measure only one element at
a time. Instrument setup or operating conditions may require changing hollow cathode lamps or using
different furnace parameters for each different element to be determined. Because of the limited cali-
bration range in AAS techniques, the need for sample dilution is much greater than in AES techniques.
The first report (Greenfield et al.) about the use of an atmospheric pressure inductively coupled
plasma (ICP) for element analysis via AES was published in England in 1964.
At the same time, Velmer Fassel and colleagues at Iowa State University refined the technique
and made it practical for laboratory use. By 1973, ICP was promoted as the most popular technique
in analytical emission spectrometry because of its low detection limits, long linear working ranges,
and freedom from interference.
12.2 GENERAL CHARACTERISTICS OF ICP-AES

Emission spectroscopy using ICP is a rapid, sensitive, and convenient method for the determination of
elements, including metals, in solution. All matrices, including groundwater, aqueous samples, extracts,
wastes, soils, sludges, sediments, and other solid wastes require digestion prior to analysis. (Sample
preparation procedures are discussed in Chapter 15.) Routine determination of 70 elements can be made
by ICP-AES at concentration levels below 1 mg/l. Table 12.1 lists recommended wavelengths and cor-
responding estimated detection limits. The detection limits are provided as a guide for instrument lim-
its. In reality, method detection limits are sample dependent and vary according to the sample matrix.
Detection limits, sensitivity, and optimum ranges of metals vary by matrix and instrument model.

The ICP method measures element-emitted light by optical spectrometry. Samples are nebulized and
the resulting aerosol is transported to the plasma torch. Element-specific, atomic-line emission spec-
tra are produced by radio-frequency inductively coupled plasma. The spectra are dispersed by a grat-
ing spectrometer, and the line intensities are monitored by photomultiplier tubes. The background
must be measured adjacent to analyte lines on samples during analysis.
An ICP source consists of a flowing stream of argon gas ionized by an applied radio frequency
field that typically oscillates at 27.1 MHz. This field is inductively coupled to the ionized gas by a
water-cooled coil surrounding a quartz torch that supports and confines the plasma (see Section
12.2.3). A sample aerosol is generated in an appropriate nebulizer and spray chamber and enters the
plasma through an injector tube located in the torch (Section 12.3.1). The sample aerosol is injected
directly into the ICP, subjecting the constituent atoms to temperatures of about 6000 to 8000 K.
Because this procedure results in almost complete dissociation of molecules, significant reduction in
chemical interferences is achieved. The high temperature of the plasma excites element-specific
atomic-line-emission spectra. The spectra are dispersed by a grating spectrometer, and the intensi-
ties of the lines are monitored by photomultiplier tubes.
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Inductively Coupled Plasma Atomic Emission Spectroscopy 163
TABLE 12.1
Recommended Wavelengths and Estimated Instrumental
Detection Limits for ICP
Element Wavelength (nm)a Estimated DLb (µg/l)

Aluminum 308.215 45
Antimony 206.833 32
Arsenic 193.696 53
Barium 455.403 2
Beryllium 313.042 0.3
Boron 249.773 5
Cadmium 226.502 4
Calcium 317.933 10
Chromium 267.716 7
Cobalt 228.616 7
Copper 324.754 6
Iron 259.940 7
Lead 220.353 42
Magnesium 279.079 30
Manganese 257.610 2
Molybdenum 202.030 8
Nickel 231.604 15
c
Potassium 766.491
Selenium 196.026 75
Silicon 288.158 58
Silver 328.068 7
Sodium 588.995 29
Thallium 190.864 40
Vanadium 292.402 8
Zinc 213.856 2
a
The wavelengths listed are recommended because of their sensitivity and overall accept-
ance. Other wavelengths may be substituted if they can provide the needed sensitivity and
are treated with the same corrective techniques for spectral interference. In time, other el-
ements may be added as more information becomes available and as required.
b
The estimated detection limits are provided as a guide for an instrument limit. In reality,
method detection limits are sample dependent.
c
Highly dependent on operating conditions and plasma position.
The ICP provides an optically “thin” source that is not subject to self-absorption except in very high
concentrations. Thus, linear dynamic ranges of four to six orders of magnitude are observed for many
elements. The efficient excitation provided by the ICP results in low concentrations. Coupled with the
extended dynamic range, such efficiency permits effective multielement determination of metals.
12.2.2 PERFORMANCE CHARACTERISTICS

The ICP-AES technique is applicable to the determination of a large number of elements at micro-
gram-per-liter (ppb) levels. For precise quantitation, the element’s concentration should be 50 to 100
times higher than the detection limit. ICP-AES analysis is not recommended for low-level concen-
tration elements or elements that are naturally entrained into the plasma from sources other than the
L1572_C12 5/23/02 1:38 PM Page 164
analyzed sample, such as traces of argon and CO2 from argon gas, H2 and O2 when water is the sol-
vent, C from organic solvent, and H2, O2, and N2 from air. ICP-AES should also not be used to deter-
mine elements whose atoms have very high excitation energy requirements, such as fluorine, chlo-
rine, the noble gases, and synthetic elements. Table 12.2 lists elements by suggested and alternate
wavelengths, estimated detection limits, calibration concentrations, and typical upper limits for lin-
ear calibration.
One advantage of ICP-AES is its long linear dynamic range. (Linear dynamic range is discussed
in Section 7.5.1.) This range makes possible instrument calibration to a one- or two-point curve.
Another advantage is that less sample dilution is necessary. With this technique, operators can deter-
mine a large number of elements over a wide range of concentrations, and many elements can be de-
termined in the same analytical run. The precision and accuracy of ICP-AES results are sufficient for
TABLE 12.2
Suggested Wavelengths, Estimated Detection Levels, Alternate Wavelengths, Calibration
Concentrations, and Upper Limits
Suggested Estimated Alternate Calibration Upper Limit

Wavelength Detection Wavelength Concentrationa Concentration
Element (nm) (µg/l) (nm) (mg/l) (mg/l)
Al 308.22 40 237.32 10.0 100
Sb 206.83 30 217.58 10.0 100
As 193.70 50 189.04b 10.0 100
Ba 455.40 2 493.41 1.0 50
Be 313.04 0.3 234.86 1.0 10
B 249.74 5 249.68 1.0 50
Cd 226.50 4 214.44 2.0 50
Ca 317.93 10 315.89 10.0 100
Cr 267.72 7 206.15 5.0 50
Co 228.62 7 230.79 2.0 50
Cu 324.75 6 219.96 1.0 50
Fe 259.94 7 238.20 10.0 100
Pb 220.35 40 217.00 10.0 100
Li 670.78 4c — 5.0 100
Mg 279.08 30 279.55 10.0 100
Mn 257.61 2 294.92 2.0 50
Mo 202.03 8 203.84 10.0 100
Ni 231.60 15 221.65 2.0 50
K 766.49 100c 769.90 10.0 100
Se 196.03 75 203.99 5.0 100
SiO2 212.41 20 251.61 21.4 100
Ag 328.07 7 338.29 2.0 50
Na 589.00 30c 589.59 10.0 100
Sr 407.77 0.5 421.55 1.0 50
Tl 190.86b 40 377.57 10.0 100
V 292.40 8 — 1.0 50
Zn 213.86 2 206.20 5.0 100
a
Other wavelengths may be substituted if they provide the needed sensitivity and are corrected for spectral interference.
b
Available with vacuum or inert gas purged optical path.
c
Sensitive to operating conditions.
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FIGURE 12.1 ICP zones: IR, induction region; PHZ, preheat-

ing zone; IRZ, initial radiation zone; and NAZ, normal analyti-
cal zone.
most analytical work. Compared to other analytical atomic spectrometry techniques, ICP-AES is
subject to the lowest number of interferences. Interferences are discussed in Section 12.4.
12.2.3 ICP DISCHARGE

Argon gas is directed through a torch consisting of three concentric tubes made of quartz or another
suitable material. A copper coil, called the load coil, surrounds the top end of the torch and is con-
nected to a radio-frequency (RF) generator. When RF power (typically 700–1500 W) is applied to
the load coil, an alternating current moves back and forth (oscillates) within the coil at a rate corre-
sponding to the frequency of the generator (27–40 MHz). Oscillation of the current in the coil
causes RF electric and magnetic fields to be set up in the area at the top of the torch. With argon gas
being swirled through the torch, a spark is applied to the gas causing electrons to be stripped from
argon atoms. These electrons are then caught up in the magnetic field and accelerated by it. Adding
energy to the electrons by the use of a coil in this manner is known as inductive coupling. These
high-energy electrons collide with other argon atoms and produce more electrons. This collisional
ionization of the argon gas continues and breaks down the gas into a plasma consisting of argon
atoms, electrons, and ions, forming the inductively coupled plasma discharge. This ICP discharge
is then sustained by the torch and load coil, as RF energy is continually transferred to it during the
inductive coupling process.
FIGURE 12.2 Temperature regions of typical ICP discharge.

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The ICP discharge is very intense, brilliant white, and teardrop-shaped. Figures 12.1 and 12.2
illustrate the ICP zones and plasma temperature regions, respectively.
12.2.3.1 Plasma Functions

12.2.3.1.1 Desolvation
The first function of the high-temperature ICP is to remove the solvent from the sample droplet or
desolvate, leaving the sample as microscopic salt particles.
12.2.3.1.2 Vaporization and Atomization
The salt particles decompose into gas molecules and then dissociate into atoms. These processes
occur in the preliminary zone (PHZ) of the ICP (see Figure 12.1).
12.2.3.1.3 Excitation and Ionization
As discussed previously, an electron of any atom or ion can be promoted to a higher energy level by
an excitation process during which it emits characteristic radiation. This process occurs in the initial
radiation zone (IRZ) and in the normal analytical zone (NAZ) (see Figure 12.2).
12.2.3.1.4 Emission Measurement
The light emitted by the excited atoms and ions is measured in the NAZ region of the plasma. The
emitted light of diverse wavelengths is measured with a polychromator and detected by a photomul-
tiplier tube. The wavelengths are separated by a monochromator.
12.3 ICP-AES INSTRUMENTATION

In ICP-AES, the sample is usually transported into the instrument in the form steam from a liquid
sample. The liquid is converted into an aerosol and transported to the plasma where it is vaporized,
atomized, and excited or ionized. The emitted radiation is collected and measured. The major com-
ponents and layout of a typical ICP-AES instrument are illustrated in Figure 12.3.
Transfer
Optics
Radio
Frequency Spectrometer
Generator PMT
ICP
Torch
Argon Nebulizer
Microprocessor
Spray and
Chamber Electronics
Pump
To Waste
Sample
Computer
FIGURE 12.3 Major components and layout of a typical ICP-AES instrument.

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12.3.1 SAMPLE INTRODUCTION

12.3.1.1 Nebulizers
Nebulizers convert a liquid into an aerosol that can be transported to the plasma, where it is desolved,
vaporized, atomized, ionized, and excited. The type of nebulizer used depends on the samples to be
analyzed as well as the equipment.
12.3.1.2 Pumps
The sample solution is pumped to the nebulizer; with the help of a series of rollers, the solution is
pushed through the tubing. The tubing is made of materials that are not affected by acidic solutions,
organic solvents, and hydrogen fluoride. The instrument’s operating manual includes instructions for
the use of proper tubing. The peristalting pump tubing is the only part of an ICP system that typically
requires frequent replacement. The tubing should be checked daily for wear, which is indicated by
permanent depressions that can be detected by running one’s fingers over the tubing.
12.3.1.3 Spray Chambers

Between the nebulizer and torch is the spray chamber, as seen in Figure 12.3. The chamber removes
large droplets from the aerosol before it enters the plasma and smoothes out pulses. The diameter
of the slow droplets entering the plasma should be about 10 µm or smaller. These droplets consti-
tute about 1% to 5% of the sample, and the remaining 95% to 99% of the sample is drained into a
waste container.
12.3.1.4 Drains
The drain carries the excess sample from the spray chamber to the waste container and provides the
backpressure necessary to force the sample aerosol carrying the gas flow through the torch injector
tube and into the plasma discharge. If the drain system does not drain evenly or it allows bubbles to
pass through, the injection of the sample to the plasma will be disrupted and noisy emission signals
can result.
12.3.2 EMISSION PRODUCTION

12.3.2.1 Torches
The torches contain three concentric tubes for argon gas flow and aerosol injection (see Sections
12.2.1 and 12.3.1). The spacing between the two outer tubes is very narrow so that the gas flows be-
tween them at high velocity and in a spiral movement, thereby keeping the quartz walls of the tubes
cool. For this reason, the argon gas flow is also called the coolant flow or plasma flow (because the
gas flow makes the plasma). In argon ICPs, it is known as plasma gas flow, and the flow rate is 7 to
15 l/min.
The gas flow carrying the sample aerosol is injected into the plasma through a central tube called
the injector. Because this flow carries the sample to the plasma, it is called the sample flow. When
used as the nebulization gas, it is called the nebulizer flow. The flow rate is usually 1 l/min, and is
known as the auxiliary flow. The three flows are illustrated in Figure 12.4.
The most popular torches can be fitted with various injector tubes, including corrosion-resistant
ceramic injectors, injectors for analyzing organic solvents, and injectors for introducing samples con-
taining highly dissolved solids.
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Viewing Slot
Load Coil
Plasma Flow
Auxiliary Flow
Injector Tube
Nebulizer
Flow
FIGURE 12.4 Schematic of a torch used for ICP-AES.
12.3.2.2 Radio-Frequency (RF) Generators

The RF generator provides the power (generally 600–1800 W) for the plasma torch. Heat is trans-
ferred to the plasma gas through a load coil surrounding the top of the torch. The load coil is usually
made of copper tubing, and during operation it is cooled by water or gas. Most ICP-AES generators
operate at a frequency of 27 to 56 MHz.
12.3.3 COLLECTION AND DETECTION OF EMISSIONS

12.3.3.1 Transfer Optics
The emission radiation from the normal analytical zone (NAZ) of the plasma is collected by a fo-
cusing optic, such as a convex lens or a concave mirror, which transfers it onto the entrance slit of
the wavelength-dispersing device.
12.3.3.2 Wavelength-Dispersive Device

The collected emission radiation is then differentiated by elements, accomplished with a diffraction-
grating-based dispersive device. (Diffraction grating is discussed in Section 6.2.1.) This device is
simply a mirror with closely spaced lines etched into its surface, with a density of 600 to 4200 lines
per millimeter. When light strikes such a grating, the light is diffracted at an angle, which is depend-
ent on the wavelength of light and the line density of the grating. The longer the wavelength and the
higher the line density, the higher the diffraction angle will be. The grating is incorporated in a spec-
trometer. The spectrometer generates the light beam, disperses it according to wavelengths selected
by the grating, and focuses them to the appropriate exit slits. At this point, the wavelengths are passed
to the detector. A polychromator is a device comprised of several exit slits and detectors in the same
spectrometer. When only one exit slit and detector are used, the device is called a monochromator.
Both devices can be used for multielement analysis in ICP-AES instruments. Most of the analytical
emission lines in ICP-AES are in the 190 to 450 nm region. With these wavelengths, electromagnetic
radiation is absorbed by oxygen molecules; therefore, air should removed from the spectrometer by
purging it with nitrogen gas or by using a vacuum system.
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12.3.3.4 Detectors
The detector measures the intensity of the emission line. The photomultiplier tube (see Section 7.3.5)
— the most widely used detector in ICP-AES — consists of a vacuum tube containing a photocath-
ode that ejects electrons when struck by light. These electrons travel to a dynode that produces one
to five secondary electrons for every electron striking its wall. The secondary electrons strike another
diode, producing new electrons, and so on. A typical photomultiplier tube contains 9 to 16 dynode
stages. The anode in the tube collects the electrons from the last dynode. As many as 106 secondary
electrons are produced from a single photon striking the photocathode in the tube. The electrical cur-
rent at the anode is measured as the intensity of the radiation reaches the phototube. Figure 12.5 il-
lustrates how the signal produced by a photon in a photomultiplier tube is measured.
12.3.4 SIGNAL PROCESSING AND INSTRUMENT CONTROL

12.3.4.1 Signal Processing
The electrical current measured at the anode of the photomultiplier tube is converted to information
that can be passed on to a computer or immediately accessed by the analyst.
12.3.4.2 Computers and Processors

The incorporated computer is an important part of an ICP-AES instrument. Every commercial ICP-
AES instrument available today uses some type of computer to control the spectrometer and to col-
lect, manipulate, and report analytical data. The amount of control over other functions of the in-
strument varies widely from model to model.
Photocathode
hν
e-
Secondary
Electrons
Dynodes
Anode
Measurement
Device
FIGURE 12.5 Photocathode, dynode, and anode layout of photomultiplier tube.

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12.3.5 ACCESSORIES FOR ICP-AES INSTRUMENTS

12.3.5.1 Autosamplers
Typical autosamplers have a capacity of 40 to 60 samples, but some models can hold 100 samples.
Ideally, the analyst should be able to load the autosampler with standards and samples, start the
analysis, walk away, and return to find the analysis completed.
12.3.5.2 Sample Introduction Accessories

Sample introduction accessories are widely used with ICP-AES instruments. These accessories are
available directly from the instrument manufacturer or can be constructed in the laboratory.
In the hydride generation technique, the sample in dilute acid is mixed with a reducing agent,
usually a solution of sodium borohydride in diluted sodium hydroxide. The reaction of the sodium
borohydride with the acid produces atomic hydrogen. Atomic hydrogen then reacts with Hg, Sb, As,
Bi, Ge, Pb, Se, Te, and Sn in the solution to form volatile hydrides of these elements. These gaseous
compounds are separated from the rest of the reduction mixture and transported to the plasma. The
detection limits may increase by a factor of up to 1000 by using this technique.
Another technique for ICP-AES sample introduction is a graphite furnace or other electrother-
mal device to vaporize a small portion of a liquid or solid sample. In this technique, the sample in-
troduction system is replaced by a graphite furnace (see Section 9.2.4). The vapor of the sample goes
to the center of the ICP discharge in the ICP torch.
12.3.6 INSTRUMENT CARE AND MAINTENANCE

12.3.6.1 Sample Introduction and ICP Torch
Keeping the torch and sample introduction system clean and free from obstructions is important in
ensuring a smooth, uncontaminated flow of sample to the plasma. Run a blank solution for several
minutes after an analysis is completed or before the instrument is shut down for the day. After run-
ning a sample with a complex matrix, the sample introduction system requires a thorough cleaning.
Check for depressions or flat spots on the tubing. Manually stretch new tubes before placing them on
the peristaltic pump head. Make sure that the tubing is appropriate for the sample type.
12.3.6.2 Nebulizer
Make sure that the nebulizer is not clogged or leaking. When checking the aerosol for a uniform spray
pattern, be sure to use deionized water and wear eye protection.
12.3.6.3 Drain System

The drain system should be filled with liquid to the level that will provide the proper backpressure
for the nebulizer gas flow. Waste from the spray chamber should flow smoothly.
12.3.6.4 Torch
Check for leaks caused by damaged quartz tubes. Deposits on the torch should be removed. Check
and clean the clogged injector after analyzing samples with high levels of particulates or dissolved
solids. When analyzing organic-based samples, check and remove carbon deposits from the torch
and injector.
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12.3.6.5 RF Generator
The RF load coil should be checked for corrosion or leakage. The high-voltage wires and other parts
of the ignition system must be checked and replaced if corroded. The power amplifier tubes must be
checked, but replacement should be performed only by professionals. Always be sure that the labo-
ratory exhaust venting system for the ICP torch box is functioning properly before igniting the
plasma. Harmful ozone, toxic combustion products, and metal fumes may accumulate in the labora-
tory if not vented properly.
12.3.6.6 Spectrometer
Windows should be regularly inspected and carefully cleaned or replaced as necessary. Periodically
check wavelength calibration as described in Section 6.7.
12.3.6.7 Computer
Conduct regular routine computer maintenance, such as cleaning disk drives and air filters. If data
files are stored on the hard disk, “clean up” the data file directories by erasing files or transferring
them to disks.
12.3.7 VERIFICATION OF INSTRUMENT PERFORMANCE

Several tests are available to verify that the instrument is working properly. Some of these tests
should run on a daily basis, and some should be used as diagnostic tests to verify problems indicated
by erratic results. Before running tests, wait for the instrument to warm up properly. The warm-up
usually takes 30 to 60 min.
12.3.7.1 Bullet Test

The visual bullet test should be performed on a daily basis. A solution of yttrium or sodium in a con-
centration of 1000 mg/l or more is introduced into the system. The emission should produce a so-
called “bullet” in the center of the ICP discharge. The mere presence of the bullet indicates that the
sample aerosol is reaching the plasma, while the vertical position of the bullet in the discharge is an
indicator of the gas flow and RF power settings.
12.3.7.2 Signal Intensity

The number of emission counts (called signal intensity) for an element with known concentration is
frequently measured, because the emission count for a given concentration may vary from day to day.
12.3.7.3 Background Equivalent Concentration (BEC)

The BEC is an indicator of relative sensitivity for an emission line. A BEC of a higher-than-normal
value often indicates problems with the efficiency of the sample introduction system, although it can
be due to a number of causes.
12.3.7.4 Precision
The precision of an argon emission line is sometimes used as a diagnostic test for the RF generator.
Precision is discussed in Section 13.9.
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12.3.7.5 Detection Limits

Detection limits may also be used for diagnostic purposes. Detection limits and measurements are de-
scribed in Section 13.8. The measured detection limits alone do not serve as an indicator of an instru-
ment’s performance, unless the measurement is combined with a series of other, more specific tests.
12.3.7.6 Wavelengths
Because UV/Vis spectrometers are subject to drift, ensure that the spectrometer is calibrated properly
in terms of wavelength prior to ICP analysis. In some instruments, calibration is performed by the in-
strument software at the beginning of the analysis, but some instruments require manual checking.
12.4 INTERFERENCES IN ICP-AES

Most interferences are of spectral origin. Other types of interference are often the result of high con-
centrations of certain elements or compounds in the sample matrix and can be easily compensated
for in most cases.
12.4.1 SPECTRAL INTERFERENCES AND CORRECTIONS

Light emission from spectral sources other than the element of interest may increase the apparent sig-
nal intensity. Spectral interferences are caused by (1) overlap of a spectral line from another element;
(2) unresolved overlap of molecular spectra; (3) background contribution; and (4) stray light from the
line emission of high-concentration elements.
12.4.1.2 Spectral or Background Interferences

The following interferences are well known to users of the ICP-AES technique:
• Simple and sloping background shift

• Direct spectral overlap
• Complex background shift
12.4.1.2.1 Correction of Spectral Interferences

• Alternate analytical wavelengths: Avoid line overlaps by selecting alternate analytical
wavelengths.
• Interelement correction: Measure the emission intensity of the interfering element at an-
other wavelength and calculate a correction factor (Section 12.6.8). This factor should
apply to determine the correct result. This technique is often useful in correcting the sim-
ple, sloping, and complex background shifts. Analyte concentration equivalents arising
from interference at the 100-mg/l level are presented in Table 12.3. The interference is ex-
pressed as analyte concentration arising from 100 mg/l of interference element. For ex-
ample, assume that As is to be determined (at 193.696 nm) in a sample containing ap-
proximately 10 mg/l of Al. According to Table 12.3, 100 mg/l of Al would yield a false sig-
nal for As equivalent to approximately 1.3 mg/l. Therefore, the presence of 10 mg/l of Al
would result in a false signal for As equivalent to approximately 0.13 mg/l. The interfer-
ence effects must be evaluated for each individual instrument.
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TABLE 12.3
Analyte Concentration Equivalents Arising from Interference at the 100-mg/l Level
Interferencea,b
Metal Wavelength (nm) Al Ca Cr Cu Fe Mg Mn Ni Tl V
Al 308.215 — — — — — — 0.21 — — 1.4
Sb 206.833 0.47 — 2.9 — 0.08 — — — 0.25 0.45
As 193.696 1.3 — 0.44 — — — — — — 1.1
Ba 455.403 — — — — — — — — — —
Be 313.042 — — — — — — — — 0.04 0.05
B 249.773 0.04 — — — 0.32 — — — — —
Cd 226.502 — — — — 0.03 — — 0.02 — —
Ca 317.933 — — 0.08 — 0.01 0.01 0.04 — 0.03 0.03
Cr 267.716 — — — — 0.003 — 0.04 — — 0.04
Co 228.616 — — 0.03 — 0.005 — — 0.03 0.15 —
Cu 324.754 — — — — 0.003 — — 0.05 — 0.02
Fe 259.940 — — — — — — 0.12 — — —
Pb 220.253 0.17 — — — — — — — — —
Mg 279.079 — 0.02 0.11 — 0.13 — 0.25 — 0.07 0.12
Mn 257.610 0.005 — 0.01 — 0.002 0.002 — — — —
Mo 202.030 0.05 — — — 0.03 — — — — —
Ni 231.604 — — — — — — — — — —
Se 196.026 0.23 — — — 0.09 — — — — —
Si 288.158 — — 0.07 — — — — — — 0.01
Na 588.995 — — — — — — — — 0.08 —
Tl 190.864 0.30 — — — — — — — — —
V 292.402 — — 0.05 — 0.005 — — — 0.02 —
Zn 213.856 — — — 0.14 — — — 0.29 — —
a
Dashes indicate that no interference was observed even when interferences were introduced at the following levels:
Al, 1000 mg/l; Mg, 1000 mg/l; Ca, 1000 mg/l; Mn, 200 mg/l; Cr, 200 mg/l; Tl, 200 mg/l; Cu, 200 mg/l; V, 200 mg/l;
and Fe, 1000 mg/l.
b
The figures recorded as analyte concentrations are not observed concentrations. To obtain those figures, add the
listed concentrations to the interference figure.
12.4.2 NONSPECTRAL INTERFERENCE

12.4.2.1 Physical Interference
Physical interference is associated with nebulization and transportation processes. Changes in the
physical properties of samples, such as viscosity and surface tension, in highly dissolved solids and
high-acid concentrations can cause significant errors. Physical interferences may be compensated
with sample dilution or by the standard addition technique (see Section 7.7.1). Samples consisting of
highly dissolved solids may cause salt buildup at the tip of nebulizer. Using prehumidified argon for
each sample nebulization is helpful.
12.4.2.2 Chemical Interferences

Chemical interference is caused by molecular compound formation, ionization effects, and sample va-
porization. Chemical interference is highly dependent on the sample matrix and the element of interest.
These conditions are easily minimized by careful selection of operating conditions. Similar to physical
interference, chemical interference may be compensated by using matrix-matched standards or by
using the standard additions method.
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12.5 REAGENTS AND STANDARDS

12.5.1 CHEMICALS, STANDARDS, AND REAGENTS
• Chemicals and reagents should be ultra-high-purity grades, except as noted.
• Dry all salts at 105°C for 1 h and store in a desiccator before weighing.
• Use deionized water prepared by passing it through at least two stages of a deionization
process for preparing standards, reagents, and dilutions. Criteria and checks of laboratory
pure-water quality are covered in Section 13.4.
12.5.2 ACIDS
• Hydrochloric acid, HCl concentrate, and 1+1
• Nitric acid, HNO3 concentrate, and 1+1
Add 500 ml of HNO3 concentrate to 400 ml of water and dilute to 1 liter.
12.5.3 STANDARD STOCK SOLUTIONS

Standard stock solutions can be purchased or prepared from chemicals or metals. See Appendix H
for recipes of these stock solutions. Store metal stock solutions at room temperature with a record of
arrival, date opened, and expiration date (see Section 13.6.1).
12.5.4 MIXED CALIBRATION STANDARD SOLUTIONS

• Prepare mixed calibration standard solutions by combining appropriate volumes of the
stock solutions in 100-ml volumetric flasks.
• Add 2 ml 1:1 HNO3 and 10 ml 1:1 HCl and dilute to 100 ml with distilled water. Mix well.
Store the mixed standards in FEPs (fluorocarbon or unused polyethylene bottles).
Concentrations of standards can change with aging! Verify concentrations by using quality con-
trol sampling and monitor weekly for stability. Some typical combinations of mixed standards fol-
low, although alternative combinations are acceptable.
Mixed standard solution I: Be, Cd, Mn, Pb, Se, and Zn

Mixed standard solution II: Ba, Co, Cu, Fe, and V
Mixed standard solution III: As, Mo, and Si
Mixed standard solution IV: Al, Ca, Cr, K, Na, and Ni
Mixed standard solution V: Ag, B, Mg, Sb, and Tl
Note: If the addition of Ag to the recommended acid combination results in an initial precipitation,
add 15 ml of distilled water and warm the flask until the solution clears. Cool and dilute to 100 ml
with distilled water. The Ag concentration should be limited to 2 mg/l, which is stable for 30 days.
Higher concentrations of Ag require additional HCl.
12.5.5 BLANKS
12.5.5.1 Calibration Blank
Measure 2 ml 1+1 HNO3 and 10 ml 1+1 HCl and dilute to 100 ml with laboratory pure water. Prepare
a sufficient quantity to be used to flush the system between standards and samples.
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12.5.5.2 Method Blank

Carry a reagent blank through the entire sample preparation procedure. Prepare with the same acid
contents and concentrations as the sample solutions.
12.5.6 INSTRUMENT CHECK STANDARD

Prepare the standard by combining compatible elements at concentrations equivalent to the midpoint
of respective calibration curves.
12.5.7 INTERFERENCE CHECK SOLUTION

This solution is prepared to contain known concentrations of interfering elements that will provide
an adequate test for correction factors (Section 12.6.8). Spike the sample with the element of inter-
est at the approximate concentration of ten times the instrument detection limits.
12.5.8 QUALITY CONTROL STANDARDS

Obtain a certified aqueous reference standard from an outside source and prepare according to the in-
structions provided by the supplier. Use the same acid matrix as the calibration standards.
12.5.9 METHOD QUALITY CONTROL SAMPLE

Carry quality control sample (Section 12.5.8) through the sample preparation procedure.
12.6 PROCEDURE
12.6.1 SAMPLE PREPARATION
Preparation depends on the physical and chemical characteristics of the samples. Sample preparation
methodology is discussed in Chapter 15.
12.6.2 INSTRUMENT SETUP AND OPERATION

1. The instrument should be warmed up for at least 30 min.
2. Set up the instrument with proper parameters. Because of differences among types and
models of instrumentation, follow the manufacturer’s instructions. Program the instrument
using the computer software provided with the instrument. Establish instrument detection
limits, optimum background correction positions, linear dynamic range, and interferences
for each analytical line.
3. Before making analytical measurements, take the necessary steps to determine that the in-
strument is set up and functioning properly. (Instrument maintenance and performance
verification are discussed in Sections 12.3.6 and 12.3.7.)
4. Calibrate the instrument, using the typical mixed standard solutions. Flush the system with
the calibration blank (Section 12.5.5.1) between each standard. For concentrations greater
than 500 µg/l, an extended flush time of 1 to 2 min is recommended.
5. Before analyzing samples, reanalyze the highest mixed calibration standard as if it is a
sample. Concentration values obtained should not deviate by more than ±5% from the ac-
tual value or from the established control limit, whichever is lower.
6. Flush the system with the calibration blank for at least 1 min. Run the quality control sam-
ple (Section 12.5.8). The concentration value should not deviate more than ±5% of the
original value.
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7. Begin each sample run with the calibration blank (Section 12.5.5.1), and then analyze the
method blank (Section 12.5.5.2). This permits a check for contamination of sample prepa-
ration reagents and procedures.
8. Flush the system with the calibration blank (Section 12.5.5.1) for at least 1 min before the
analysis of each sample. Analyze samples while alternating them with a calibration blank.
If carryover is observed, repeat rinsing until proper blank values are obtained.
9. Analyze the quality control check standard (highest calibration standard) and quality con-
trol sample (Section 12.5.8) once per ten samples. If agreement is not within ±5% of the
expected values, terminate analysis of samples, correct the problem, recalibrate the in-
strument, and analyze the quality control sample again to confirm proper recalibration.
Reanalyze one or more of the samples analyzed just before termination of the analytical
run. Results should agree to within ±5%; otherwise, all samples analyzed after the last ac-
ceptable quality control test must be reanalyzed.
10. Analyze the quality control sample (Section 12.5.8) during each run. Use this analysis to
verify accuracy and stability of the calibration standards. If any result is not within ±5%
of the certified value, prepare new calibration standards, and recalibrate the instrument. If
this does not solve the problem, prepare a new stock solution and new standards, and re-
calibrate the instrument again.
11. Analyze the method quality control sample (Section 12.5.9) with every run. Results devi-
ating more than ±5% of the certified value indicate losses or contamination during prepa-
ration.
12. When analyzing a new or unusual sample matrix, verify that positive or negative nonlin-
ear interferences do not exist. If the element is present above a 1 mg/l concentration, di-
lute the sample with a calibration blank. Results from the analysis of dilution should be
within ±5% of the original result. If the result is below 1 mg/l or not detected, spike the di-
gested sample with 1 mg/l. Recovery should be within 95 and 105%.
12.6.3 INSTRUMENT CALIBRATION

Set up the instrument as described in Section 12.6.2, items 1 through 3. Calibrate the instrument ac-
cording to the manufacturer’s recommended procedure using the typical mixed standard solutions
described in Section 12.5.4. Flush the system with the calibration blank (Section 12.5.5.1) between
each standard. Aspirate each standard or blank for a minimum of 5 sec after reaching the plasma but
before beginning signal integration. Rinse with the calibration blank for at least 60 sec between each
standard to eliminate any carryover from the previous standard. For boron concentrations greater
than 500 mg/l, extended flush times of 1 to 2 min may be required.

1. Before analyzing samples, analyze the instrument check standard (Section 12.5.6).
Concentration values obtained should not deviate by more than ±5% from the actual val-
ues or the established control limits, whichever is lower. If they do, follow the recommen-
dations of the instrument manufacturer to correct for this condition.
2. Flush the system with the calibration blank (Section 12.5.5.1) solution for at least 1 min.
3. Analyze the method blank (Section 12.5.5.2).
4. Analyze samples, alternating with analysis of the calibration blank (Section 12.5.5.1).
Rinse for at least 60 sec with diluted acid between samples and blanks. Examine each
analysis of the calibration blank to verify that no carryover has occurred. If carryover is
observed, repeat the rinsing until proper blank values are obtained.
5. Make appropriate dilutions or concentrations of the sample to determine concentrations
beyond the linear concentration range.
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12.6.5 INSTRUMENT QUALITY CONTROL

1. Analyze the instrument check standard (Section 12.5.6) once per ten samples to determine
significant instrument drift. If agreement is not within ±5% of the expected value or within
the established control limits, whichever is lower, terminate the analysis of samples, cor-
rect the problem, and recalibrate the instrument.
2. Confirm proper recalibration by analyzing the instrument check standard.
3. Reanalyze one or more of the samples analyzed just before termination of the analytical
run. Results should agree to within ±5%; otherwise, all samples analyzed after the last ac-
ceptable instrument check standard analysis must be reanalyzed.
4. Analyze quality control sample (Section 12.5.8) with every run to verify the accuracy and
stability of the calibration standard. If any result is not within ±5% of the calibrated value,
prepare a new calibration standard and recalibrate the instrument. If this does not correct
the problem, prepare a new stock solution and a new calibration standard and repeat cali-
bration.
12.6.6 METHOD QUALITY CONTROL

Analyze the method quality control sample (Section 12.5.9) during every run. Results should agree
within ±5% of the certified value. Greater discrepancies may reflect losses or contamination during
sample preparation.
12.6.7 TEST FOR MATRIX INTERFERENCE

When analyzing a new or unusual sample matrix, verify that positive and negative nonlinear inter-
ference effects are not operative. If the element is present at a concentration above 1 mg/l, use serial
dilution with a calibration blank. Results from analyses of a dilution should be within ±5% of the
original result. If the result is below 1 mg/l or not detected, use a postdigestion addition equal to 1
mg/l. Recovery of the addition should be between 95% and 105% or within the established control
limits of two standard deviations around the mean. If a matrix effect causes test results to fall outside
the critical limits, complete the analysis after diluting the sample to eliminate the matrix effect while
maintaining a detectable concentration at least twice the detection limit, or applying the standard ad-
dition method.
12.6.8 CALCULATIONS AND CORRECTIONS

12.6.8.1 Blank Correction
12.6.8.1.1 Calibration Blank
See Section 12.5.5.1. Subtract the result of an adjacent calibration blank from each sample result
to calculate a baseline drift correction. Make certain that the used calibration blank has not been
contaminated.
12.6.8.1.2 Reagent Blank or Method Blank
See Section 12.5.5.2. Use the result of the method blank analysis to correct reagent contamination.
12.6.8.2 Dilution and Concentration Correction

If the sample was diluted or concentrated, correct the result accordingly. In the case of dilution, the
result should be multiplied by the dilution factor (final volume/initial volume). For example, if the
original result was 0.20 mg/l and the sample was diluted 5 times, the corrected result will be 0.20 ×
5 = 1.00 mg/l.
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Because of low concentration of a metal in a sample, the digestion technique is used and the sam-
ple will be concentrated. For example, an original 100-ml sample was cooked down to 10-ml final
volume. The reading of the concentrated sample was 0.06 mg/l, so the final result is 0.06/10 = 0.006
mg/l or 6 µg/l.
12.6.8.3 Correction for Spectral Interference

Correct for spectral interference (see Section 12.4.1) by using computer software supplied by the
manufacturer or by using the manual method based on interference correction factors. Determine in-
terference correction factors by analyzing single-element stock solutions of appropriate concentra-
tions under conditions that match as closely as possible those used in the sample analysis. Calculate
the correction factors by using the following equation:
C.F. = A/B (12.1)
where
A = difference between the observed concentration in the stock solution and the
observed concentration in the blank.
B = actual concentration.
All results should be reported in micrograms per liter with up to three significant figures.
12.7 QUALITY CONTROL

All quality control data should be maintained and available for easy reference and inspection. For
complete quality control criteria, see Chapter 13. The quality control check process for ICP analysis
is discussed in Section 12.6.2, items 6 through 12.
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Quality Control in
13 Metals Analysis

Quality control procedures are necessary to ensure that the obtained analytical data and reported val-
ues are correct. Validation and approval of analytical data are based on a well-designed and regularly
applied quality assurance/quality control (QA/QC) program. The components of this program are di-
vided into a management (QA) and a functional (QC) part. Quality Assurance is a laboratory opera-
tion program of specified standard procedures that are aimed at producing data of defensible quality
and highly reliable reported results. Quality Control consists of a set of measures within a sample
analysis methodology to ensure that the process is controlled.
Laboratory personnel develop their own QA/QC program, which should be delineated in a
QA/QC manual. The program should be strictly enforced, continually reviewed, and updated as
needed. Large laboratories typically have a QC control officer or group independent of laboratory
management charged with oversight of the QA/QC program.
Quality assessment is the mechanism for verifying that a laboratory system is operating within
acceptable limits. This mechanism consists of all activities aimed at providing assurance that the
overall quality control job is being done effectively. Each laboratory develops its own QA program,
which should be delineated in a QA/QC manual and should be comprehensive enough to apply to
most operations. This program should be continually reviewed and updated as needed. The labora-
tory should also have a separate QA “project plan” for each project. Understanding the QA program
helps analysts to be responsible participants in the laboratory system in order to produce defendable,
precise, and accurate analytical data.
13.2 GLASSWARE USED IN METALS ANALYSIS

The mainstay of a modern analytical laboratory is a highly resistant borosilicate glass, such as Pyrex
or Kimax. Corning-brand glassware is highly resistant to alkalis and practically boron free. Raysorb-
or Lo-actinic-brand glassware is recommended for light-sensitive solutions. Stoppers and cups
should be carefully selected: Do not use metal caps or rubber-stoppered bottles for metal solutions!
13.2.1 VOLUMETRIC GLASSWARE

Volumetric glassware is used for accurate volume measurements; therefore, it should meet the Class
A glassware specification and be permanently marked with “A” and the temperature at which cali-
bration was made. Carefully check glassware for TC (to contain) or TD (to deliver) marks, and use
them accordingly. Not suitable, incorrectly used, or improperly cleaned glassware endangers the
quality of analytical results.
179
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13.2.2 CLEANING GLASSWARE

When cleaning glassware for metals analysis, use the following guidelines. Always use appropriate
detergent, such as Liquinox, Alconox, or an equivalent.
1. Remove all labels or marks from the glassware (using acetone is acceptable).
2. Wash with hot soapy water. Use appropriate detergent. Use brush to scrub inside the glass-
ware. (Do not use a brush with any metal parts.)
3. Rinse thoroughly with hot tap water.
4. Rinse thoroughly with distilled water.
5. Rinse with 1:1 HCl.
6. Rinse with 10% HNO3.
7. Rinse with laboratory-grade water.
8. Volumetric class A glassware should not be dried by heating!
9. Store glassware to protect from contamination, dust, breakage, and chipping.
Store glassware in an area separate from the metals analysis work area to avoid contamination.
13.3 CHEMICALS
Carefully select the grade of the chemical that meets the requirements of the work to be done. Always
recheck the label of the chemical that you are using. The use of a wrong chemical can cause an explo-
sion or ruin the analytical work. Check the information carefully on the container of the chemical: name,
formula, formula weight, percentage of impurities, analytical grade, health hazards, safety codes, and ex-
piration date. Store in chemical storage room. All chemicals used for Hg analysis must be Hg-free.
13.4 LABORATORY-PURE WATER

13.4.1 QUALITY OF LABORATORY-PURE WATER
One of the most important aspects of chemical analysis is the quality of the laboratory-pure water
or reagent-grade water to be used in the preparation of standard solutions, reagents, dilutions, and
blank analysis.
13.4.1.1 Distilled Water

Distillation is the procedure in which the liquid is vaporized, recondensed, and collected. Distilled water
quality depends on the type of still and the quality of the feed water. Deionized feed water is preferred.
13.4.1.2 Demineralized or Deionized Water

This type of water is purified in a mixed-bed exchanger. Commercial resin-purification trains that
produce superior water quality are available.
13.4.1.3 Redistilled Water

This type of water is prepared by redistilling single-distilled water from an all-borosilicate-glass
apparatus.
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Quality Control in Metals Analysis 181
13.4.1.4 Reagent Water

Reagent water is a sample that conforms to ASTM grades II, III, or IV (see Section 13.4.2).
13.4.1.5 Analyte-Free Water

This type of water is free of the substance analyzed.
13.4.1.6 Reagent-Grade Water

This is the highest-quality, laboratory-pure water. It is prepared by passing distilled water through an
activated carbon cartridge to remove dissolved organic materials. It is then passed through two deion-
ized cartridges to remove dissolved inorganic substances. Finally, it is passed through membrane fil-
ters to remove microorganisms and any particulate matter with a diameter as large as 0.22 µm. This
kind of high-quality water is commercially available and used in AA, GC work, and tissue culturing,
among other things.
13.4.2 TYPES OF LABORATORY-PURE WATER

The type of laboratory-pure water used depends on the analytical work. For metals analysis, the cri-
terion is analyte-free water with an ASTM-grade type II classification. ASTM International (ASTM,
formerly the American Society for Testing and Materials) specifies the various grades of laboratory-
pure water.
13.4.2.1 Type I Water

Type I water has no detectable concentration of the compound or element to be analyzed at the de-
tection limit of the analytical method. Use type I water in test methods requiring minimum interfer-
ence and bias and maximum precision. It is prepared by distillation, deionization, or reverse osmo-
sis treatment of feed water, followed by polishing with a mixed-bed deionizer and passage through a
0.2-µm-pore-size membrane filter. type I water cannot be stored without significant degradation;
therefore, produce it continuously and use immediately after processing.
13.4.2.2 Type II Water

Type II is the same as type I water but without passage through a 0.2-µm-membrane filter. This
type is used in tests in which the presence of bacteria can be tolerated. Type II water is recom-
mended for metals analysis. It can be stored, but keep storage to a minimum. Store only in mate-
rials that protect the water from contamination, such as Teflon or glass for organic analysis and
plastic for metals analysis.
13.4.2.3 Type III Water

Type III water may be used for washing glassware, preliminary rinsing of glassware, and as feed
water for preparation of higher-quality water. Storage is similar to type II water.
The quality of laboratory-pure water should be checked regularly. Parameters and monitoring
frequency for quality checks are listed in Table 13.1; an example of recommended documentation of
quality checks is presented in Table 13.2.
13.5 FIELD QUALITY CONTROL

The quality of data resulting from sampling activities depends on the following major activities:
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• Collecting representative samples

• Use of appropriate equipment
• Proper sample handling and preservation
• Proper chain-of-custody and sample identification procedure
• Proper QA and QC in the field
13.5.1 FIELD QA/QC PROGRAM

The field QA/QC program consists of the following areas and corresponding documentation:
1. Sample collection methodology called “field standard operation procedure” (FSOP) with
special procedures: Each method must be accompanied by method numbers, method ref-
erence, method detection limits, and accepted limits for precision and accuracy. These
methods should be approved by the Environmental Protection Agency (EPA) and DEP.
2. Field QC requirements
3. Procedures to record and process data
4. Procedures to review and reduce data based on QC results
5. Processes to validate field measurement data for reporting purposes
6. Procedures to calibrate and maintain field instruments and equipment
7. Qualification and training of sampling personnel to attain proficiency in the following areas:
• Determination of the best representative sample site
• Use of proper sampling techniques by choosing grab or composite sampling, selection
of the appropriate equipment, use of proper sample preservation, and sample identification
• Use of appropriate data recording techniques and reporting form
• Calibration and maintenance of field instruments and equipment
• Use of QC samples such as duplicate, split, and spiked samples
• After the training program, the fresh-sample collector must be involved in sampling
activities under the direction of a more experienced person for at least 1 month prior to
assuming field responsibility; special training workshops are available for training of
sampling personnel.
13.5.2 CRITERIA FOR FIELD QC CHECKS

Sampling operations must also be supported by a well-designed and reliable quality assurance pro-
gram, including QC checks.
13.5.2.1 Equipment Blanks

Equipment blanks are used to detect contamination from sampling equipment. At least one equip-
ment blank should be collected for every 20 samples per parameter group and for each matrix. Each
type of equipment used in sampling must be accompanied by an equipment blank. This blank is pre-
pared in the field before sampling begins by using the precleaned equipment and filling the
appropriate container with analyte-free water. Preservation and documentation should be the same as
for the collected samples. If equipment is cleaned on site, then additional equipment blanks should
be collected for each equipment group.
13.5.2.2 Field Blanks

Field blanks are collected at the end of the sampling event. Fill an appropriate sample container with
analyte-free water and preserve and document in the same manner as the collected samples.
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TABLE 13.1
Quality Check of Laboratory-Pure Water
Parameter Monitoring Frequency Limit

Conductivity D 1–2 µmhos/cm
pH D 5.5–7.5 unit
Total organic carbon A <1.0 mg/l
Trace metal, single A <0.05 mg/l
(Cd, Cr, Cu, Ni, Pb, Zn)
Trace metal, total A <1.0 mg/l
(Cd, Cr, Cu, Ni, Pb, Zn)
Ammonia, as NH3–N M <0.1 mg/l
Free chlorine, Cl2 M <0.1 mg/l
Heterotrophic count
Fresh water M <1000 cnt/ml
Stored water M <10,000 cnt/ml
Water suitability test A Ration: 0.8–3.0
Note: A = annually; M = month; D = daily; cnt = count (bacterial).
TABLE 13.2
Documentation of Laboratory-Pure Water Quality
Het.
Cond. NH3
Date pH TOC Cd Cr Cu Ni Pb Zn Bact. In.
(µmhos/cm) as N
(c/ml)
Note: Parameters are reported in mg/l, except as noted.

Cond. = conductivity, µmhos/cm; TOC = total organic carbon; Cd = cadmium; Cr = chromium; Cu = copper; Ni = nickel;
Pb = lead; Zn = zinc; NH3–N = nitrogen ammonia; Het. Bact. = heterotrophic bacteria count, count/ml; In. = initial of the
logger.
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13.5.2.3 Trip Blank

The purpose of trip blanks is to verify contamination that may occur during sample collection and
transportation, as a result of improperly cleaned sampling containers, contaminated reagents, airborne
contamination during transportation, and so on. Trip blanks are blanks of analyte-free water prepared
by the laboratory and transported to the field that remain unopened during the sampling and are then
transported back to the laboratory with the collected samples. These blanks should be properly labeled
and documented. Trip blanks are usually collected with volatile organic compound (VOC) samples.
13.5.2.4 Duplicates
Duplicates are samples collected at the same time from the same source (called field duplicates) or
aliquots of the same sample that are prepared and analyzed at the same time (laboratory duplicates).
Duplicate samples are analyzed to calculate measurement precision. During each independent sam-
pling event, at least one sample or 10% of the samples, whichever is greater, must be collected for
duplicate analysis. This requirement applies to each parameter group and each matrix sampled.
13.5.2.5 Field-Spiked Samples

Field-spiked samples are environmental samples that contain specific added concentrations of vari-
ous parameters of interest. Spiked samples are used to measure the performance of the complete an-
alytical system, including interference from the sample matrix. Field preparation and transportation
to the laboratory of a spiked sample should be similar to other samples, and the spiked sample should
be marked as FSp (field-spiked sample). If spiked duplicates are collected, they are identified as FSp1
and FSp2. Spiked samples are selected according to a specific requirement, previous evaluation of
the sample site, or an on-site inspection.
13.5.2.6 Split Samples

Split samples are replicas of the same sample. Split samples are given to two independent laborato-
ries for analysis.
13.6 INSTRUMENT CALIBRATION

Calibration and standardization of analytical systems are necessary to ensure that the produced data
are accurate.
13.6.1 CALIBRATION STOCK AND STANDARD SOLUTIONS

13.6.1.1 Calibration Stock Solutions
Calibration stock solutions are either commercially available or “house prepared” by the laboratory.
Records should be maintained for both types of stock solutions as illustrated in Figures 13.1 and 13.2.
Calibration stock solutions used for metals analysis are stored at room temperature. In the case of pur-
chased stock, the applicable holding time is indicated by the given expiration date. House-prepared
stock should be renewed when instrument response is not satisfactory.
13.6.1.2 Calibration Standard Solutions

Calibration standard solutions are prepared from calibration stock solutions by appropriate dilution. A
log form for preparation of calibration standards is illustrated in Figure 13.3. The form should contain
the concentration of the stock solution, dilution technique for the desired concentration, date and
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Name and concentration: __________________________________________________________________

Test for use: ____________________________________________________________________________
Source: ________________________________________________________________________________
Lot number: ____________________________________________________________________________
Date received:___________________________________________________________________________
Date opened:____________________________________________________________________________
Expiration date: _________________________________________________________________________
Manufacturer’s certification: _______________________________________________________________
Storage:________________________________________________________________________________
Date of disposal:_________________________________________________________________________
Mode of disposal: ________________________________________________________________________
Remarks:_______________________________________________________________________________
______________________________________________________________________________________
______________________________________________________________________________________
_____________________________ _____________________________
Signature of logger Date
FIGURE 13.1 Documentation log form for purchased calibration stock and standard solutions.
Name and concentration: _________________________________________________________________

Test of use: ____________________________________________________________________________
Source of chemical used:
Name and formula:____________________________________________________________________
Grade:______________________________________________________________________________
Lot number: _________________________________________________________________________
Source: _____________________________________________________________________________
Date received:________________________________________________________________________
Date opened: ________________________________________________________________________
Preparation procedure:
Temperature and drying time of chemical prior to preparation: _________________________________
Volume prepared: _____________________________________________________________________
Quantity of chemical used: _____________________________________________________________
Remarks: _____________________________________________________________________________
_____________________________________________________________________________________
_____________________________________________________________________________________
Date: ______________________________Signature: __________________________________________

Date: ______________________________Approval by supervisor: _______________________________
FIGURE 13.2 Documentation log form for preparation of calibration stock solution.
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signature of the preparer, and, if applicable, holding time and mode of storage. Calibration standards for
metals analysis should be preserved with 0.5% HNO3. Concentrations such as 100 ppm and 10 ppm stan-
dards may be stored at room temperature up to 1 month but should be replaced when readings of con-
centration values show decline. Documentation for storage and preparation of the standards must be
available. Every time calibration is performed, it is recommended that working standards be prepared
fresh.
13.6.2 CALIBRATION CHECK SOLUTIONS

13.6.2.1 Continuing Calibration Standard (CCS)
The CCSs are used to ensure calibration accuracy during every analytical run. The CCS represents
the value of the midpoint initial calibration standard. It must run immediately after the standard curve
is established, during the analytical batch analysis (at a frequency of 5%), and after the last sample
is analyzed. The deviation from the original value should be within ±5%.
13.6.2.2 Calibration Verification Standard (CVS)

The CVS is a known-value standard used to verify that the standards and calibration are accurate and
to confirm the calibration curve. It should be certified (purchased from the EPA or another source)
or independently prepared by a source other than the source of the calibration standards. The value
is accepted within a ±10% deviation from 100% recovery. The log form for preparation of the CVS
is illustrated in Figure 13.4.
Test:_________________________________________________________________________________________
Optimum Calibration Range: _____________________________________________________________________
Stock Solution, Concentration: ____________________________________________________________________
Final Volume of Standards, ml:____________________________________________________________________
Concentration of Standards Volume Stock Used
________________________________ _______________________________
________________________________ _______________________________
________________________________ _______________________________
________________________________ _______________________________
________________________________ ______________________________
Concentration of Continuing Calibration Standard: ____________________________________________________
_____________________________________________________________________________________________
Date of Preparation: ____________________________________________________________________________
Expiration Date: _______________________________________________________________________________
Storage Description (if applicable): ________________________________________________________________
_____________________________________________________________________________________________
_____________________________________________________________________________________________
Date: _____________________________Signature:__________________________________________________
Date: ______________________________Approval by Supervisor: ______________________________________
FIGURE 13.3 Documentation log form for preparation of calibration standards.

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13.6.2.3 Preparation Blank (Prep Blank) and Laboratory

Control Standard (LCS)
When samples go through pretreatment (digestion, extraction, filtration, etc.) prior to analysis, pre-
treatments should be verified and the effects of sample preparation monitored. To support these
measures, a blank and standards should be prepared and analyzed together with the sample. The
preparation blank is a volume of analyte-free water processed through the sample preparation pro-
cedure. The LCS is the same concentration as the CVS, except that it is carried through the prepara-
tion and analysis procedure in the same way as the samples. Acceptable recovery is a ±15% devia-
tion from 100% recovery.
13.6.3 INITIAL AND CONTINUING CALIBRATION

Calibrations are performed at the beginning of the analysis to ensure that the instrument is working prop-
erly. This initial calibration has to be proven during the analytical process by continuing calibration.
When continuing calibration fails to meet acceptance criteria, the initial calibration should be repeated.
Calibrations must be performed according to specifications of a particular analytical method.
13.6.3.1 Initial Calibration

An initial calibration is determined for each parameter tested and is based on the instrument re-
sponses for different concentration ranges of the calibration standards. The number and optimum
concentration range of calibration standards used in a particular analytical method are specified in
Name and Concentration _____________________________________________________________________

Storage ___________________________________________________________________________________
Outside Source
Manufacturer:____________________________________________________________________________
Certification available: _____________________________________________________________________
Date received: ___________________________________________________________________________
Expiration date: __________________________________________________________________________
Storage: ________________________________________________________________________________
In-House Prepared
Name, formula, and grade of the chemical used:_________________________________________________
_______________________________________________________________________________________
Lot number: _____________________________________________________________________________
Date received: ___________________________________________________________________________
Date opened: ____________________________________________________________________________
Expiration date: __________________________________________________________________________
Preparation procedure: _____________________________________________________________________
_______________________________________________________________________________________
_______________________________________________________________________________________
Signature of Logger: __________________________________________Date:__________________________

Approval by Supervisor: _______________________________________Date:__________________________
FIGURE 13.4 Documentation log form for preparation of calibration verification standards or quality
control check standards.
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the approved methodology and described by the laboratory’s standard operation procedure (SOP). If
this information is not available, then a minimum of one blank and three standards must be utilized
for calibration. Instrument calibration varies according to the type and model of the equipment.
Detailed operation and calibration procedures for each instrument are available in laboratory SOPs
and the manufacturer’s instruction. Initial calibration is based on the instrument response for differ-
ent concentrations of calibration standards against calibration blanks.
Standards are prepared by analysts or highly reliable suppliers. The concentration of the stan-
dards should be bracketed in the optimum concentration range given by the analytical method. The
number of standards is recommended by the method or instrument manufacturer. When the number
of standards is not known, a three-standard calibration is satisfactory.
The concentration of the “high standard” is the upper level of the optimum range, the concentra-
tion of the “middle-point standard” is half of the highest standard, and the value of the “low-level
standard” is five times lower than the highest standard. The response of the instrument should be lin-
ear with the concentration of the introduced standards. The concentration of the standards and the re-
sponse of the instrument are plotted on a calibration curve (see Section 6.6), or the instrument soft-
ware automatically prepares the curve. After the calibration curve is prepared, it should be approved
through calculation of the corresponding correlation coefficient via linear regression. The coefficient
should be greater than 0.9998; otherwise, a new calibration must be performed. Calculation results
should be available for inspection at any time.
13.6.3.2 Continuing Calibration

At a 5% frequency, or once per analytical batch, the initial calibration must be approved by continu-
ing calibration. (Samples analyzed under the same method sequence and using reagents of the same
lot number — i.e., samples comprising a single analytical batch — should have similar matrices.)
Continuing calibration includes analysis of the calibration blank, CCS, and CVS, with the above-
mentioned frequency and acceptance levels.
13.6.4 ACCEPTED CALIBRATION

Preparation of the calibration curve with the accepted correlation coefficient, the CCS within the
proper range, and the CVS with the correct percentage of recovery are the criteria of the appropriate
initial calibration for the instrument and analytical system. If these criteria are not met, the initial cal-
ibration should be repeated and samples analyzed before the criteria failure must be analyzed again.
13.6.5 OUTLINE OF CALIBRATION PROCEDURE

1. Establish the calibration curve by using a blank and a number of calibration standards in
the optimum range as dictated by the analytical method.
2. Determine acceptance or rejection of the curve by calculating the correlation coefficient.
3. Run the CCS to verify the curve. The result must be within ±5% of the verified value.
4. Run the CVS. As stated in Section 13.6.2.2, it must be supplied by a source different from
that of the calibration standards. The initial calibration is accepted if the result is within
±10% of the true value.
5. If the analytical method includes sample pretreatment (e.g., digestion), a preparation blank
and a treated CVS (called the LCS) should be incorporated into the analytical run. Results
within ±15% of the true value are accepted.
6. Analyze ten samples (including reagent blanks, spikes, and duplicates).
7. After the analysis of the ten samples, check the curve again with the CCS. It must be within
±5% of the verified value.
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8. The accepted curve should be certified again with the CVS. If the result is within ±10% of
the true value, continue measuring the samples.
9. If the CCS or CVS fails to meet the criteria, the run must be stopped and a new initial cal-
ibration performed. Samples analyzed before the failed standards were discovered must be
analyzed again. If verification of the initial calibration is satisfactory, proceed with analy-
sis and repeat the same verification at a 5% frequency.
13.6.6 SPECIAL CALIBRATION CRITERIA IN METALS ANALYSIS

13.6.6.1 Atomic Absorption Spectrophotometer (AAS)
Calibration is based on a three-point standard curve (low, middle, and high level) in the optimum lin-
ear range as specified per analyte in the respective methodology. This is performed every time the in-
strument is used, or after failure of continuing calibration standards. Calculation of the calibration
curve is done by computer software using linear regression. The curve is checked to ensure linear cor-
relation of greater than 0.9998. Complete the initial calibration by checking the curve with CCS and
CVS, and using continuing calibration check in the same manner as outlined above in Section 13.6.5,
numbers 3 through 9.
13.6.6.2 Inductively Coupled Plasma (ICP) Analyzer

By monitoring several wavelengths, either all at once or in a programmed sequence, many elements
can be determined in a single automated analysis. The ICP analyzer offers a significant speed ad-
vantage for determination of metals in environmental samples. Calibration is performed with the use
of mixed, multielement calibration standards. The number of calibration standards and the calibra-
tion technique are defined by the instrument manufacturer. Initial calibration and checking with con-
tinuing calibration are the same as described in Section 13.6.5.
13.6.7 SUMMARY OF DEFINITIONS RELATED TO CALIBRATION

13.6.7.1 Optimum Concentration Range
The optimum concentration range is the range in which the calibration curve remains linear. This
range is defined by the analytical method and varies according to instrumentation.
13.6.7.2 Calibration Stock Solution

Calibration stock solution is a high-concentration solution of the analyte. It is commercially avail-
able or prepared by the laboratory.
13.6.7.3 Intermediate Standard Solution

This standard is diluted from the stock solution (Section 13.6.7.2) to obtain a concentration suitable
to dilute the calibration standards.
13.6.7.4 Calibration Standards

Calibration standards are solutions of precise concentrations prepared by diluting the calibration
stock or the intermediate standard solution. The number of standards is determined by the analytical
method and the instrument, while the concentration is determined by the given optimum range.
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13.6.7.5 Mid-Range Standard

The mid-range standard is defined as a standard in the middle of the linear range of the established
calibration curve or a standard concentration in the middle of the expected sample concentration
range, depending on the type of determination to be performed.

The calibration blank is a volume of analyte-free water used to zero the instrument. It is also run at
the end of the analytical work to check whether contamination or drift occurred.
13.6.7.7 Preparation Blank

The preparation blank is a volume of analyte-free water processed through the sample prepara-
tion procedure.
13.6.7.8 Continuing Calibration Standard (CCS)

The CCS is used to ensure calibration accuracy during each analytical run. The CCS is analyzed at
the beginning and end of the analysis and after every ten samples. The CCS concentration must be at
or near the mid-range level.
13.6.7.9 Calibration Verification Standard (CVS) or QC Check Standard

The CVS is an independently prepared standard with a concentration near the mid-level standard and
is prepared by a source other than the calibration standards source. It is analyzed at the beginning and
end at a frequency of 10% during the analysis.
13.6.7.10 Laboratory Control Standard (LCS)

The LCS is a CVS carried through the entire sample preparation and analysis process. It is used to
monitor the effects of sample preparation.
13.6.7.11 Sensitivity Check Standard

This standard is used for optimizing an AA spectrophotometer. The concentration of the standard
varies according to the analytical method and is also stated in the manufacturer’s instructions. With
this standard, the instrument must provide an absorbance reading at or near 0.200.
13.6.7.12 QC Check Samples

These samples, which are obtained from an independent source, contain a known value of the ana-
lyte. Check samples are analyzed along with a sample set of similar matrix, and the obtained results
are used to determine the accuracy of laboratory performance.
13.7 INSTRUMENT PERFORMANCE CHECK

13.7.1 ATOMIC ABSORPTION SPECTROPHOTOMETER (AAS)
13.7.1.1 Flame and Graphite
The AAS performance checks are performed every time a different metal is analyzed as part of an
analytical procedure. The performance check provides a reading of the instrument’s optimal opera-
tion, and thus is an indicator of deterioration in the lamps or the spectrophotometer. Performance is
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measured via a sensitivity check standard, a concentration of a particular metal dictated by the ana-
lytical method. The absorbance of this standard should be 0.200. If it differs by more than ±10%, the
instrument is not performing correctly and must be corrected. Sensitivity standard concentrations for
the FAAS and GrAAS techniques are presented in Tables 8.3 and 9.4, respectively.
13.7.2 INDUCTIVELY COUPLED PLASMA ANALYZER (ICP)

While ICP-AES analysis is often simple to perform, obtaining good analytical result requires atten-
tion to details that could influence analysis outcomes. Besides preparing samples carefully and se-
lecting the proper hardware and operating parameters, the analyst should ensure that the instrument
is properly set up and maintained. Specific information on maintenance and performance tests can
usually be found in manufacturer’s operator manuals. Guidelines for the care and maintenance of
these instruments are discussed in Section 12.3.6.
Checking the performance of the instrument before beginning an analysis is recommended. In
some cases, such as certain environmental analyses, the analysis protocol may specify performance
tests that must be run before, during, and after an analysis. Such protocols are often quite rigorous,
as the validity of the data produced must be able to stand up in a court of law if challenged. General
tests that are often used to verify that an ICP-AES instrument is performing properly are listed below.
Some of these tests are quite simple and should be performed on a daily basis. Other tests are more
rigorous and can be used as diagnostics when malfunctions are suspected.
13.7.2.1 Warm-Up Time

Before analytical work begins, the instrument should be warmed up. The recommended warm-up
time is 30 to 60 min.
13.7.2.2 Visual Bullet Test

This test can be performed on a daily basis. The analyst introduces 1000 mg/l or more of an element
whose atomic emission produces a well-defined “bullet” in the center of the ICP discharge. The mere
presence of the bullet indicates that the sample aerosol is reaching the plasma, while the vertical po-
sition of the bullet in the discharge is an indicator of the gas flow and RF power settings being used.
Sodium and yttrium are often used in this test.
13.7.2.3 Signal Intensity

The number of emission counts for a given concentration of an element is often used as a quick in-
strument diagnostic. This test is usually more useful for trend analysis than as an absolute indicator
of performance because the emission counts may vary somewhat from day to day.
13.7.2.4 Background Equivalent Concentration (BEC)

The BEC is an indicator of relative sensitivity for an emission line. A BEC value higher than normal
often indicates problems with the efficiency of the sample introduction system.
13.7.2.5 Precision
The precision of an argon emission line is used as a diagnostic test for the RF generator. Five to ten
measurements for a strong emission line are used to calculate precision, and this figure may be ex-
pressed as %CV (correlation of variation) or %RSD (relative standard deviation).
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13.7.2.6 Detection Limits

The causes of measured detection limits outside expected range are numerous. Running this test
along with other specific tests is recommended.
13.7.2.7 Ion/Atom Ratio

The ratio of emission intensity of an ion line to emission intensity of an atom line is an indicator of
relative excitation in the plasma.
13.7.2.8 Wavelength/Peak Alignment

Prior to sample analysis, make sure that the spectrometer is calibrated properly in terms of wave-
length. Calibration is performed manually or automatically by the instrument software at the begin-
ning of an analysis.
13.8 LABORATORY QC CHECKS

Laboratory QC checks include all practices and activities that ensure accuracy and precision of the
analytical measurements. QC checks serve as tools for approval of generated analytical data.
Laboratory staff should follow all method-specific QC requirements. Guidelines for basic controls of
chemical measurements are summarized below.
13.8.1 BLANKS
A calibration blank is used to establish the analytical curve. It is prepared by measuring 2 ml of 1:1
HNO3 and 10 ml of 1:1 HCl into a 100-ml volumetric flask (see Section 13.2 for preparation of glass-
ware for metals analysis) and dilute to the mark with analyte-free water. Prepare a sufficient quantity
to flush the system between running standards and samples.
13.8.1.2 Reagent Blank or Method Blank

A reagent blank is used to correct possible contamination caused by reagents used in processing sam-
ples prior to sample analysis. If the analytical method includes any pretreatment (digestion, distilla-
tion, etc.) one analyte-free water blank must be processed and analyzed the same way as the samples.
13.8.2 DUPLICATE SAMPLES

Duplicate samples are collected at the same time and from the same source as analytical samples but
are submitted and analyzed as separate samples. The analyst does not know that they are duplicates.
Duplicate samples are used to determine precision of analytical performance. Analyze one duplicate
in every 20 samples.
13.8.2.1 Field Duplicates

Duplicate field samples are collected at the same time from the same source and are submitted and
analyzed as separate samples.
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13.8.2.2 Laboratory Duplicates

Laboratory duplicates are aliquots of the analytical sample that are prepared and analyzed at the
same time.
13.8.3 SPIKES
13.8.3.1 Spiked Sample or Matrix Spike
Specific concentrations of the parameters of interest are added to spiked samples. Spiked samples are
used to measure the performance of the complete analytical system, including chemical interferences
from the sample matrix. A small quantity of a known concentration of analyte stock solution is added
to the sample (or aliquot). Always use highly concentrated stock solutions, so that a small quantity
of spike added to the sample does not change sample volume. Always add spike solution before sam-
ple preparation.
Water samples are thoroughly mixed by shaking the sample container before measuring out the
sample aliquot. The spike addition should produce a minimum level of ten times and a maximum
level of 100 times of the instrument detection limit (IDL).
Use the following formula to calculate the volume of the spike addition, concentration of the
spike solution, desired spike concentration, and the volume of the sample spiked:
c1v1 = c2v2 (13.1)
where
c1 = (c2v2)/v1
v1 = (c2v2)/c1
c2 = (c1v1)/v2
v2 = (c1v1)/c2
where
c1 = concentration of the spike stock solution.
v1 = the unknown.
c2 = desired spike concentration.
v2 = volume of the sample before spiking.
If the analytical set involves multiple matrices, matrix spikes should be prepared for all matrix
types. Analyze one per set at a rate equivalent to 5% of all samples.
Calculate the percent recovery on the spike (%Rsp) by using the following formula:
%Rsp = (spiked sample value – sample value) × 100/added spike value (13.2)
13.8.3.2 Reagent Water Spike

Analyte-free water is spiked with the analyte and is prepared in the same way as the samples. A
reagent water spike is used to monitor analytical method effectiveness. Run at 5% frequency.
Concentration and preparation are the same as described for matrix spike (Section 13.8.3.1). The rec-
ommended level of the spike addition is five times the method quantification limit.
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13.8.3.3 Duplicate Matrix Spike Sample

Duplicates of matrix spike samples (instead of duplicate samples) may be used to check the preci-
sion of the analytical system.
13.8.4 CALIBRATION CHECK STANDARDS

Calibration check standards are also part of proper calibration criteria. See Section 13.6.
13.8.5 BLIND QC CHECK SAMPLES

Qualiy Control check samples (also known as reference materials) are obtained from an independent
source with known analytical levels. The analyst is not informed of the true concentration value of
the sample. QC check samples measure and validate the analytical system and analyst performance.
Accuracy is expressed as percent recovery (see Formula 13.6). Blind check samples are run on a
semiannual basis and are part of the QA report.
13.8.6 PERFORMANCE EVALUATION SAMPLES

Reference materials obtained from an independent source for which the level(s) of analytes have
been validated are used in performance evaluations. Performance testing evaluates a laboratory’s
ability to produce a specified quality of data and is used in obtaining certification and contract qual-
ification.
Evaluation of results is an essential part of performance testing. Each participant should be in-
formed of his or her performance in relation to an acceptable standard. Information on each analyte
should include the true value, acceptance range, reported value, and the evaluation as “accepted,”
“not acceptable,” or “check for error.” Laboratory managers conduct overviews of results, initiate
corrective action as needed, and document all steps of remedial actions.
13.8.7 INTERFERENCE CHECK

Verify interelement and background correction factors at the beginning and end of the analytical run
or twice during every 8-h work shift, whichever is more frequent. This verification is accomplished
by analyzing the interference check sample. Review interelement correction!
13.9 DETECTION LIMITS

Detection limits are the smallest concentration of the analyte of interest that can be measured within
a specific probability of significance.
13.9.1 METHOD DETECTION LIMIT (MDL)

The MDL is the smallest concentration of the analyte of interest that can be measured and re-
ported with 98% confidence that the concentration is greater than zero. MDL determination steps
are outlined below.
1. Estimate the MDL by using the minimum detection concentration described by the ana-
lytical method.
2. Prepare 1 liter of standard by adding the analyte to analyte-free water to create a concen-
tration close to the estimated MDL.
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3. Analyze seven portions of the solution and calculate the standard deviation (SD) of the re-
sults.
4. In a Student’s t table (see Table 13.3), select the t value for 6 degrees of freedom (df) at
the 98% level (df = n − 1, or 7 − 1 = 6 in this case). The value of t at the 98% level is 3.14.
5. The calculation of the MDL follows:
MDL = SD × 3.14 (13.3)
In this formula, SD is the standard deviation calculated in step 3.
13.9.2 INSTRUMENT DETECTION LIMIT (IDL)

The IDL is the concentration of the analyte that produces a signal greater than five times the signal-
to-noise ratio of the instrument. An operating analytical instrument usually produces a signal greater
than three standard deviations of the mean noise. IDL determination follows:
1. Analyze analyte-free water seven times and record instrument signals.

2. Calculate the standard deviation of the seven instrument responses.
3. Calculate the IDL:
TABLE 13.3
Student’s t Table
df 80% t.90 90% t.95 95% t.975 98% t.99 99% t.996 99.73% t.9985
1 3.078 6.314 12.706 31.821 63.657 235.80
2 1.886 2.920 4.303 6.965 9.925 19.207
3 1.638 2.353 3.182 4.541 5.841 9.219
4 1.533 2.132 2.776 3.747 4.604 6.620
5 1.476 2.015 5.571 3.365 4.032 5.507
6 1.440 1.943 2.447 3.143 3.707 4.904
7 1.415 1.895 2.365 2.998 3.499 4.530
8 1.397 1.860 2.306 2.896 3.355 4.277
9 1.383 1.833 2.262 2.821 3.250 4.094
10 1.372 1.812 2.228 2.764 3.169 3.975
11 1.363 1.796 2.201 2.718 3.106 3.850
12 1.356 1.782 2.179 2.681 3.055 3.764
13 1.350 1.771 2.160 2.650 3.012 3.694
14 1.345 1.761 2.145 2.624 2.977 3.636
15 1.341 1.753 2.131 2.602 2.947 3.586
16 1.337 1.746 2.120 2.583 2.921 3.544
17 1.333 1.740 2.110 2.567 2.898 3.507
18 1.330 1.734 2.101 2.552 2.878 3.475
19 1.328 1.729 2.093 2.539 2.861 3.447
20 1.325 1.725 2.086 2.528 2.845 3.422
25 1.316 1.708 2.060 2.485 2.787 3.330
30 1.310 1.697 2.042 2.457 2.750 3.270
40 1.303 1.684 2.021 2.423 2.704 3.199
60 1.296 1.671 2.000 2.390 2.660 3.310
1.282 1.645 1.960 2.326 2.576 3.000
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IDL = SD × 3 (13.4)
In this formula, SD is the standard deviation of the average signal of the instrument in steps
1 and 2.
13.9.3 PRACTICAL QUANTITATION LIMIT (PQL)

The PQL is the smallest concentration of the analyte of interest that can be reported with a specific
degree of confidence. This limit has been proposed as the lowest level achievable among laboratories
within specified limits during routine laboratory operations. The PQL is significant because differ-
ent laboratories will produce different MDLs even though they are using the same analytical proce-
dures, instruments, and sample matrices. The concentration related to the PQL is about five times the
MDL and represents a practical and routinely achievable detection limit with a relatively high cer-
tainty that any reported value is reliable. To determine the PQL, take the standard deviation (SD)
from the determination of MDL and multiply by 10. The ten standard deviations correspond to an un-
certainty factor of ±30% in the measured value at the 98% confidence limit.
PQL = SD × 10 (13.5)
where SD is the standard deviation of MDL (see Section 13.9.1).
13.10 ACCURACY AND PRECISION

Satisfactory analytical data are accurate and precise.
13.10.1.1 Accuracy
Accuracy is the degree of agreement of a measured value with the true or expected value of the quan-
tity of interest. Accuracy is measured and expressed as percent recovery (%R) and calculated ac-
cording to the following formula:
%R = analytical value × 100/true value (13.6)
13.10.1.2 Precision
Precision is the degree of mutual agreement among individual measurements as the result of repeated
applications under the same conditions. Precision measures the variation among measurements and
is expressed in different ways.
13.10.1.3 Standard Deviation (SD)

Calculate by using a calculator or the following formula:
SD = E(x − X)2/n − 1 (13.7)
where
E = sum
X = mean of measurements
x = sum of measurements
n = number of measurements
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13.10.1.4 Relative Standard Deviation (RSD)

The RSD is derived in four steps:
1. Calculate standard deviation (SD).

2. Calculate the mean of the measurements (x).
3. Calculate the coefficient of variant (CV) (standard deviation divided by the mean):
CV = SD / x (13.8)
4. Calculate the RSD:
RSD = CV × 100 (13.9)
13.10.1.5 Relative Percent Difference (RPD)

The RPD is the difference between duplicate values divided by the average of the duplicate values
and multiplied by 100:
RPD = (A − B)/[(A + B)/2] × 100 (13.10)
or
RPD = (A − B)/(A + B) × 200 (13.11)
13.10.2 QUALITY CONTROL DELINEATION FOR ACCURACY AND PRECISION

Calculated accuracy (%R) and precision (SD, RSD, or RPD) values are used in determination of QC
limits for each parameter.
13.10.2.1 Accuracy Control Limits

1. Collect 20 data points for the parameter of interest.
2. Calculate the mean (x) and the standard deviation (SD).
3. Calculate the accuracy of QC limits as %R.
Warning limits (WLs) = x ± 2 SD

Upper warning limit (UWL) = x + 2 SD
Lower warning limit (LWL) = x − 2 SD
Control limits (CLs) = x ± 3 SD
Upper control limit (UCL) = x + 3 SD
Lower control limit (LCL) = x − 3 SD
When %R data are outside the warning limits, the analytical system is critical (approaching an
out-of-control situation) and may require corrective action. Data falling outside the control limits in-
dicate an out-of-control system; analysis must be stopped and corrective action taken. Samples ana-
lyzed after the failed QC check sample should be analyzed again.
13.10.2.2 Precision Control Limits

1. Collect 20 data points of expressed precision (see Section 13.9.) for the parameter of
interest.
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2. Calculate the mean (x) and the standard deviation (SD).

3. Calculate the QC limits for precision. Because the minimum value for precision is zero,
the lower limits should always be zero.
Warning limits (WLs) = 0 − (x + 2 SD)

Upper warning limit (UWL) = x + 2 SD
Lower warning limit (LWL) =0
Control limits (CLs) = 0 − (x + 3 SD)
Upper control limit (UCL) = x + 3 SD
Lower control limit (LCL) =0
Any value falling above the warning limit should be interpreted as a signal that the system is crit-
ical and may indicate the need for corrective action. Data falling outside the control limits indicate
that the system is out of control.
13.10.2.3 Confidence Limit or “Target Limit” for Precision and Accuracy

At the completion of any analysis, the calculated precision and accuracy values are documented on
the related QC charts and recorded on summary log forms (illustrated in Tables 13.4, 13.5, and 13.6).
Based on these collected statistical results, QA “target limits” should be established for each analyte
per matrix. These limits serve as a confidence range for precision and accuracy values. This calcula-
tion consists of the following steps:
1. Collect a minimum of 20 data points for precision determination or 20 data points for ac-
curacy determination.
2. Calculate the mean of these values (x) and the corresponding standard deviation (SD).
3 Calculate the confidence interval (CI) according to the following formula:
CI = x ± [(t × SD)/n] (13.12)
The value of t (Student’s t) depends on the degrees of freedom (df = n − 1) for the 98% confi-
dence level (see Table 13.3). For example, assume that the average confidence-level value of the 20
data points for %R is 98% and the standard deviation is 5.26:
x = 98%
SD = 5.26
n = 20
df = n − 1 = 19
t = 2.593
CI = 98 + (2.539 × 5.26)/4.47 = 101

CI = 98 − (2.539 × 5.26)/4.47 = 95
The confidence interval or “target limit” for accuracy is 95–101%.
13.10.3 QUALITY CONTROL CHARTS

Control charts are statistical tools for monitoring the performance of a particular task on a continu-
ing basis and have become very useful in demonstrating statistical control. Both accuracy and preci-
sion control charts should contain the name of the laboratory, the test parameter, analytical method
(method number with reference), range, and calculated standard deviation. All initial data used to
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TABLE 13.4
Monitoring Form for Precision (RPD) Values
ANALYTE ________________________METHOD _____________________MATRIX __________________________
Unit, values are expressed:_________________________________________________________________________
Sample value Duplicate

Date RPD % Control limit Remark Sign.
(A) value (B)
Note: RPD = relative percent difference. RPD = [(A – B)/(A + B)/2)] × 100 or [(A – B/A + B)] × 200.
TABLE 13.5
Monitoring Form for Accuracy (% Recovery) Values
QC check QC check
Date sample true sample % Recovery Control limit Remark Sign.
value measured value
Note: % Recovery (%R) = (measured value/true value) × 100.

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TABLE 13.6
Monitoring Form for Spike Recovery (%Rsp) Values

Spiked
Sample
Spike added sample
Date value % Recovery Control limit Remark Sign.
(SA) value
(SV)
(SSV)
Note: %Rsp = [(SSV – SV)/SA] × 100.
prepare the control limits are established by the analytical methodology and should be less than 5%
outside the upper and lower warning limits.
Quality Control charts are used on a daily basis. Each analytical method has established accuracy
and precision control limits according to the control charts that are used to determine the acceptabil-
ity of data on a continuous basis. The response to an out-of-control event must be immediate, and all
conditions and corrective actions must be documented. This report includes the out-of-control test
parameter, date, description of the QC problem, and necessary corrective action. Once the out-of-
control condition has been corrected, QC requirements are reapplied until satisfactory data points
have been plotted on the control chart.
13.10.3.1 Accuracy Control Chart

The accuracy control chart monitors the percent recovery with the standard deviation as the limiting
control. The control chart is prepared for each test parameter after 20 determinations have been per-
formed. The mean is plotted with the warning control limits of ±2 SDs (standard deviations) and
upper and lower control limits of ±3 SDs. In other words, the upper and lower warning limits are
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defined as the limits that would encompass 95% of the measured values for percent recovery, and the
upper and lower control limits are defined as the limits that would encompass 99% of the measured
values of the percent recovery.
13.10.3.2 Evaluation of Conditions in Accuracy Control Charts

The evaluation of possible conditions on accuracy control charts is illustrated in Figure 13.5.
• Condition is satisfactory: Data are variable, showing no trends and remaining within the
warning limits.
• Condition is critical: One or more points are outside the UWL and LWL; seven successive
points are in the same direction are causing either an upward or downward trend; ten suc-
cessive points are on the same side of the average value (x) of the chart.
• Condition is out of control: One or more points are outside the UCL and LCL.
PRECISION CONTROL CHARTS
Satisfactory Critical Out-of-Control

UCL
UWL
Mean
0
Satisfactory - Data are variable, showing no trends and

remaining below the warning limit
Critical - Any point above Upper Warning Limit (UWL)
- Seven (7) successive points in the same
direction causing upward trend
Out-of-Control - Any point outside the Upper Control Limit (UCL)
ACCURACY CONTROL CHARTS
Satisfactory Critical Out-of-Control

UCL
UWL
Mean
LWC
LCL
Satisfactory - Data are variable, showing no trends and remaining

within the warning limits
Critical - Any point outside the Upper and Lower Warning
Limits (UWLs and LWLs)
- Seven (7) successive points in the same
direction causing either an upward or downward
trend
- Ten (10) successive points on the same side of
the average value of the chart
Out-of-Control - Any points outside the Upper and Lower Control
Limits (UCLs and LCLs)
FIGURE 13.5 Interpretation of quality control charts.

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13.10.3.3 Precision Control Chart

The precision control chart monitors the repeatability of a measurement system, irrespective of accu-
racy. It is based on the term that was selected to express precision values. These charts are based on
results from duplicate samples after accumulating 20 data points. Precision control charts have only
upper warning and upper control limits. The lower limit for both warning and control limits is zero.
13.10.3.4 Evaluation of Conditions in Precision Control Charts

The interpretation of conditions on precision control charts is illustrated in Figure 13.5.
• Condition is satisfactory: Data are variable, showing no trends and remaining below the
warning limits.
• Condition is critical: Any one or more points are above the warning limit (WL); seven suc-
cessive points are in the same direction, causing an upward trend.
• Condition is out of control: One or more points are beyond the control limit.
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Sample Collection for

14 Metals Analysis
14.1 GENERAL CONSIDERATIONS IN SAMPLING

The quality of any analytical system depends primarily on the sample analyzed. A sample must be
representative of the environmental system from which it is taken so that chemical analysis results,
in turn, represent the system.
14.1.1 FACTORS AND REQUIREMENTS OF SAMPLING PROGRAM

TO BE CONSIDERED
• Parameters of interest with method number and references
• Duration of survey
• Frequency of sampling
• Number of samples
• Sample matrices
• Sample source
• Site identification
• Grab or composite samples (see Section 14.1.4)
• Manual and automatic sampling (see Section 14.1.5)
• Field measurements
• Quality control (QC) requirements
14.1.2 PREPARATION FOR SAMPLE COLLECTION

• Understand the sampling plan; all information should be written and discussed with field
personnel.
• Prepare, clean, and calibrate sampling equipment so that it is ready to use.
• Check, calibrate, and prepare equipment for field tests.
• Prepare sample containers.
• Prepare preservative and dispose in a safe container.
• Collect labels and markers, field notebook, pH paper, and small disposable cups to check
pH of preserved samples.
• Prepare all blanks.
• Check all calibration standards and expiration dates for freshness. If necessary, prepare
new ones.
• Check QC samples for availability, and check dates for freshness. If necessary, prepare
new ones. Determine whether sample should be spiked and discuss concentration of the
spikes. Calculate the volume of the added spike stock solution for each spiked parameter.
203
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• Collect pipets with suitable volumes and pipet bulbs.

• Collect empty bottles for splits, duplicates, and so on.
• Collect glassware for field tests and check cleanliness of glassware.
• Make sure that thermometers are stored in protective carriers to avoid breakage.
• Check spike stock solutions and check dates for freshness. If necessary, prepare new ones.
• Collect soap for cleaning sampling equipment and for washing hands, paper towels, soft
tissues, and bottles with DI (deionized) water.
14.1.3 PREFIELD PROCEDURES

Several prefield procedures must be considered prior to the sampling activities:
• Selection of proper sampling equipment (preferred materials for sampling and purging equip-
ment for metals analysis include Teflon, polypropylene or polyethylene, and stainless steel)
• Decontamination of sampling equipment
• Selection of sample bottles
• Preservative preparation
• Preparation and calibration of field analytical instruments
• Preparation of sample labels, chain-of-custody forms, field notebook, waterproof ink,
and so on
14.1.4 TYPES OF SAMPLES

14.1.4.1 Grab or Individual Samples
Samples collected at a particular time and place are called grab or individual samples. This type of
sample represents conditions at the time it was collected. Therefore, a grab sample should not be used
as a basis for decision making about pollution abatement. However, some sources are quite stable in
composition, thus single-grab samples would be considered representative.
14.1.4.2 Composite Samples

If results for an entire source system are to be reported, a series of small samples are collected in a sin-
gle container and blended for analysis. The mixing process averages variations in sample composition
and minimizes analytical effort and expense. These types of samples are called composite samples. When
a time factor is being taken into consideration, grab samples are collected at suitable intervals according
to expected changes. Composite samples reflect average characteristics during the sampling period, and
in most cases a 24-h period is standard. Subsample volume should be constant and at least 200 ml.
14.1.5 MANUAL AND AUTOMATED SAMPLE COLLECTION

14.1.5.1 Manual Sample Collection
When collecting samples for immediate field tests or when automatic samplers are not available, col-
lect samples directly into a sample container. If a sample cannot be placed directly into the container,
an intermediate vessel should be used. The intermediate container must be as clean as the sample
container and must be made from the required material for parameter of interest. The sample is col-
lected by lowering a properly cleaned device on a rope, pole, or chain into the sample medium. In
some cases, using a power or hand-operated pump is necessary to withdraw the sample. When
collecting samples for metals analysis, rinsing the sampling device three times is sufficient, except if
the bottles are prepreserved.
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Sample Collection for Metals Analysis 205
14.1.5.2 Automated Sample Collection

A wide variety of automatic samplers are commercially available. When sampling a large number of
locations, automatic samplers are more practical, help reduce human error, and are able to keep the
samples cool to 4°C during the time spent gathering samples. Automatic samplers, however, are ex-
pensive.
14.1.6 GENERAL RULES IN SAMPLING

• Samples must be collected from the least to the most contaminated sampling locations
within the site.
• Disposable latex gloves must be worn while sampling, and new, unused gloves must be
used for each separate sampling point.
• For compositing or mixing samples for metals analysis, use a stainless steel or Teflon bowl.
• Keep in mind that the order of sample collection is as follows:
1. Volatile organic compounds (VOCs)
2. Extractable organics
3. Total metals
4. Dissolved metals
5. Microbiologicals
6. Inorganic nonmetals
• For aqueous matrices, sampling equipment and containers are rinsed with the sample fluid
before the actual sample is taken, with the exception of prepreserved containers.
• A step-by-step, written sampling procedure should be available. The procedure should
contain all sample collection activities.
14.1.7 PROPER MATERIAL FOR SAMPLING DEVICES

Devices used for collecting samples for metals analysis should be made of plastic, stainless steel,
or Teflon.
14.1.8 ERRORS INTRODUCED DURING SAMPLING

Serious errors that may be introduced during sampling and storage are the contamination resulting
from improperly cleaned sampling devices and sample containers and loss of metals by absorption
or precipitation in sample containers because of failure to acidify the sample properly.
14.1.9 WASTE DISPOSAL IN THE FIELD

Wastes generated during sampling are separated into specialized and properly labeled waste con-
tainers. Laboratory- and field-generated wastes are disposed of by certified waste management com-
panies. The certificate and contract of this company should be recorded.
14.2 AUTOMATIC SAMPLERS

14.2.1 PROPER OPERATION OF AUTOMATIC SAMPLERS
To ensure proper operation of automatic samplers and thus the collection of representative samples,
correct maintenance and calibration must be followed:
• A maintenance log containing all repair information should be available.
• Prior to each field trip, check the sampler for correct operation (proper working order, bat-
teries, desiccant, etc.).
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• Before sampling, check the constant pumping volume.

• After returning from the field, check operation of sampler and repair if necessary.
14.2.2 PREPARATION OF SAMPLING EQUIPMENT

Step-by-step cleaning procedures (called decon for decontamination) should be performed. These
procedures derive from specific regulations and must be available in written form. Equipment should
be cleaned before sampling and in the field between samples. At the end of the field trip, sampling
equipment must be labeled as “rinsed, ready for house cleaning.” After being sufficiently cleaned in
the laboratory, the equipment should be labeled as “in-house cleaned, ready for field,” accompanied
by the date and the signature of the cleaner. Both house and field cleaning should be documented
properly. Detergents specified for cleaning include Alconox (or equivalent) with 5% phosphate, or
Liquinox (or equivalent), which is free of phosphates and ammonia.
The purity and reliability of the analyte-free water used for rinsing and blank preparation are
shown in results of tests performed on the blank.
14.2.2.1 In-House Cleaning of Sampling Equipment

1. Wash with hot, soapy tap water and scrub with a brush.
2. Rinse thoroughly with hot tap water.
3. Rinse with 10 to 15% nitric acid (HNO3). Acid rinses should never be applied to stainless
steel or metallic equipment.
4. Rinse thoroughly with deionized water.
5. Rinse thoroughly with pesticide-grade isopropanol.
6. Rinse thoroughly with analyte-free water.
7. Air dry completely.
8. Wrap in aluminum foil for storage and transportation.
14.2.2.2 Field Cleaning of Sampling Equipment

Use the same procedure as in-house cleaning procedure, with the exception of hot water wash and
rinse. Laboratory-pure water rinse is recommended, but optional. Rinsing with sample water is ac-
ceptable when proper cleaning of the equipment is impossible. It should be disposed of until effec-
tive cleaning is possible.
14.3 SAMPLE CONTAINERS

14.3.1 PREFERRED SAMPLE CONTAINERS
• Preferred sample containers for metals analysis are polyethylene bottles with tight, screw-
type lids.
• Borosilicate glass containers also may be used, but avoid soft glass bottles for samples
containing metals in the microgram-per-liter (ppb) range.
• Store samples for silver analysis in light-absorbing containers.
• Sample containers may be cleaned in-house or in the field or purchased from commercial
vendors as precleaned containers. The cleaning grades must meet EPA analyte-specific re-
quirements. All records for these containers (lot numbers, certification statements, date of
receipt, etc.) and their uses must be documented.
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14.3.2 PROPER CLEANING OF SAMPLE CONTAINERS

1. The soap should be metal-free Acationox or equivalent.
2. Wash bottles and caps in hot, soapy water and rinse liberally with tap water until soapsuds
are gone.
3. Rinse bottles and caps with 1+1 HCl, followed by tap water rinse.
4. Rinse bottles and caps with 1+1 HNO3.
5. Rinse three times with liberal amounts of laboratory-pure water.
6. Drain and cap tightly until used.
14.4 SAMPLE PRESERVATION

Sample preservation is necessary for all samples (40 CFR, Part 136). Sample preservation may be ac-
complished by using ready, prepreserved bottles obtained from the laboratory, but additional preser-
vatives must be available in the field if the measured pH of the preserved sample indicates that addi-
tional preservative is necessary.
If the sample is preserved in the field, the following protocols should be practiced:
• Preservative should be prepared from reagent-grade chemical.
• Fresh preservative should be used in each sampling trip.
• Preservatives transported to the field should be stored in properly cleaned plastic or Teflon
containers to avoid breakage.
• Chemicals should be segregated from sample containers to avoid accidental contamination.
• Preservatives should be added with a pipet or premeasured droppers.
• After preservation, the pH of the preserved sample should be measured. Transfer a small
quantity from the preserved and well-mixed sample into a disposable container, and de-
termine the pH by using a narrow-range pH paper. If the pH value indicates the addition
of more preservative, the preservative should be from the same source as used in the orig-
inal treatment. The amount of the additional preservative should be documented, and the
additional preservative should be added to the corresponding blank as well.
• Acid preservation should be done in a well-ventilated area to avoid inhalation of acid
fumes and toxic gases. Any unusual reaction should be noted!
• In the case of any acid spill, wipe up immediately and flush the area with a great amount
of water.
14.5 SPECIAL SAMPLING PROCEDURES

Before collecting a sample, decide on the metal fraction to be analyzed: dissolved (filterable), sus-
pended (nonfilterable), or total metals. This decision will determine whether the sample is acidified
with or without filtration.
14.5.1 TOTAL METALS

Total metals are defined as the concentration of metals in an unfiltered sample or the sum of the con-
centrations of metals in both the dissolved and suspended fractions. Preserve the sample with 3 ml
of 1+1 HNO3 or 1.5 ml of concentrated HNO3 per liter. Samples with high buffer capacity and high
alkaline samples may require more acid, as indicated by pH measurement. Samples should be trans-
ported to the laboratory without cooling.
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14.5.2 DISSOLVED METALS

Dissolved metals are defined as the concentration of metals determined in the sample after it is fil-
tered through a 0.45-µm filter. Samples must be filtered through a 0.45-µm filter prior to preserva-
tion. Filter paper should be acid washed and dried before use. After the sample is filtered, the filtrate
will be the sample for dissolved metals and acidified in the same way as for total metals.
14.5.3 SUSPENDED METALS

Suspended metals are defined as the concentration of metals determined in the portion of the sample
that is retained in a 0.45-µm filter. Unpreserved samples are filtered through a 0.45-µm filter, as men-
tioned above for the sample collection of dissolved metals, and the filter paper is retained for further
analysis of the suspended or unfilterable metals. The filter paper containing the suspended matter is
transferred to the laboratory for determination of suspended metals. Samples should be filtered in the
field, or immediately after transport to the laboratory. In the latter case, preserve the filtrate.
14.5.4 SAMPLE COLLECTION OF HEXAVALENT CHROMIUM

Materials containing hexavalent chromium (Cr6+) are sampled separately from other metals. Do not
add acid preservation to this sample; transport it to the laboratory for analysis as soon as possible.
During transportation and storage, samples should be kept at 4°C.
“No preservative added” should be clearly written on the sample label in the request for this type
of sample. Holding time is 24 h for these samples.
14.6 HOLDING TIME

Holding time for most preserved samples is 6 months. For mercury (Hg) determination, holding time
of the preserved sample is 28 days. Samples collected without preservation for the determination of
hexavalent chromium (Cr+6) can be held for only 24 h. A sample holding-time log is illustrated in
Figure 14.1.
14.7 FIELD RECORDS

Field records are taken for all data generated during sample collection. These records are kept in a
chain-of-custody form (Figure 14.2), sample label (Figure 14.3), field notebook (Figure 14.4), sam-
ple field log (Figure 14.5), preservative preparation log (Figure 14.6), and QC sample and spike
preparation log (Figure 14.7).
14.7.1 CHAIN-OF-CUSTODY
All sampling events should be documented and recorded on a chain-of-custody form. This practice
ensures that the sample is collected, transferred, stored, analyzed, and destroyed only by authorized
personnel. Each custodian or sampler must sign, record, and date the transfer. The form includes the
name of the sampling project; collector’s signature; sampling location; sampling site; sampling point,
date, and time; type of sample; number of containers; and analysis required. The chain-of-custody
form is illustrated in Figure 14.2.
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Holding Time (days) Day of Preparation Storage
Sample Matrix Analysis prep anal dispo rec prep anal dispo Sample Sign
ID Required Prepared
Sample ID = sample identification number; prep = prepared; anal = analysis; dispo = disposal; rec = received;
sign = signature of logger.
Holding Time Explanation:

prep = number of days between the date sample received and the date sample prepared
anal = number of days between the date sample prepared and the date of actual analysis
dispo = number of days between the date sample received and the date sample disposed
Storage Designations:
R. T. = room temperature in designated area
Ref. O. = refrigerator, designated for organic samples
Ref. I. = refrigerator, designated for inorganic samples
Fr. = freezer, designated for special samples
FIGURE 14.1 Sample holding-time log.
14.7.2 SAMPLE LABEL

A sample label (Figure 14.3) should be affixed to all sample containers and serves as an important
part of sample identification. The label should be waterproof, and all information should be written
in waterproof ink.
14.7.3 FIELD NOTEBOOK

The field notebook (Figure 14.4) is specially designed for fieldwork, with waterproof paper and a hard
cover. All field records should be written in waterproof ink. Errors in documents should be deleted by
a single-line cross-through, accompanied by the date and initial of the person making the correction.
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Field ID:____________________________________________________ Site Name:______________________________________________________________

210
Date Sampled Received: ______________________________________ Address:______________________________________________________________

Sampler(s): _________________________________________________ Laboratory:______________________________________________________________
5/23/02
Sample Container Description

1:41 PM
Sample Identity Date Sampled Total Remarks

Page 210
Total Number of Containers
Relinquished By: ____________ Organization: ________________________ Received By: ______________________ Organization: ________________________
Date: ______________________ Time: ________________________ Date: ______________________ Time: ________________________
Relinquished By: ____________ Organization: ________________________ Received By: ______________________ Organization: ________________________
Date: ______________________ Time: ________________________ Date: ______________________ Time: ________________________
Delivery Method: ______________________________________________ (attach shipping bills, if any)
Use extra sheets if necessary.
Environmental Sampling and Analysis for Metals
FIGURE 14.2 Chain-of-custody form.

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Field Sequence No.___________________________________________________________________________

Field Sample No.____________________Date _______________________Time ________________________
Sample Location _____________________________________________________________________________
Sample Source_______________________________________________________________________________
Preservative Used ____________________________________________________________________________
Analyses Required ___________________________________________________________________________
___________________________________________________________________________________________
Collected by ________________________________________________________________________________
Remarks ____________________________________________________________________________________
___________________________________________________________________________________________
___________________________________________________________________________________________
Final pH Checked ____________________________________________________________________________
Additional Preservative Used (If Applicable) _____________________________________________________
___________________________________________________________________________________________
FIGURE 14.3 Sample label.
Date _____________________________ Time __________________________________________________

Sampler’s name ___________________ Signature __________________________________________________
Other field people ____________________________________________________________________________
____________________________________________________________________________
____________________________________________________________________________
Sample location ____________________________________________________________________________
____________________________________________________________________________
Sample type grab __________
composite ______________________ Compositing time ________________________hr
Time interval ___________________________min
Subsample volume _______________________ml
Cond.
Preserv. Analysis DO
Sq. No. FID pH T(°C) (µmhos Cl2 Comment
container required (ppm)
/cm)
Sq. No. = sample sequence number; FID = field identification number; Cond. = conductivity; DO = dissolved
oxygen; Cl2 = chlorine, residual; ppm = parts per million (mg/l).
Field conditions:
pH check:
Additional preservative used:
Other observations:
FIGURE 14.4 Field notebook.

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Purpose of Analysis: _____________________Sample Field ID: __________________________________________

Type of Sample: ___________ Sampler: ________________________ Date/Time:__________________________
Sample
Sample Source Bottle Bottle
Site Preservative Analysis Required
Description Type No.
Number
Remarks:
* Field Measurements
FIGURE 14.5 Sample field log.
14.7.4 SAMPLE FIELD LOG AND PRESERVATIVE PREPARATION LOG

Other field records are the sample field log (Figure 14.5) and preservative preparation log
(Figure 14.6). Immediately after sampling while still at the sampling point, the correct preservation
and proper identification of samples (chain-of-custody and submittal forms, sample labels, etc.)
should be checked.
14.7.5 INFORMATION AVAILABLE IN FIELD RECORDS

The following information should be available in field records:
• Name of sample collector and field personnel
• Date and time of sampling
• Field conditions (weather, important information about the sample site)
• Description of sample location (address, exact sampling points)
• Sample type (grab, composite). If composite sample, record the time intervals, duration of
sampling, and volume of subsamples
• Requested analytical parameters, type and number of containers, preservation technique
• Preservative preparation
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Preservative ________________________________________________________________________________
Preparation Procedure_______________________________________________________________________
Date Prepared______________________________________________________________________________
Date of Expiration __________________________________________________________________________
Analyte Preserved___________________________________________________________________________
Information Related to the Chemical Used:
Name, formula, and grade of the chemical
______________________________________________________________________________________
______________________________________________________________________________________
Source of the chemical (name of manufacturer)
______________________________________________________________________________________
Lot no. of the chemical __________________________________________________________________
Date chemical received__________________________________________________________________
Date container was opened ______________________________________________________________
Expiration date _________________________________________________________________________
Storage of the chemical __________________________________________________________________
______________________________________________________________________________________
Check of Preservative _______________________________________________________________________
__________________________________________________________________________________________
________________________________ __________________________________
Preparer Supervisor
FIGURE 14.6 Preservative preparation log.
Analyte spiked _________________________________________________________________________________

Field no. of sample spiked________________________________________________________________________
Sample volume spiked ___________________________________________________________________________
Value of spike added ____________________________________________________________________________
Concentration of spike stock solution______________________________________________________________
Volume of spike stock solution added______________________________________________________________
Source of spike stock solution:
Commercial source
Manufacturer: _______________________________________________________________________
Lot no.: _____________________________________________________________________________
Date received: _______________________________________________________________________
Date expired: ________________________________________________________________________
Laboratory prepared
Date of preparation: __________________________________________________________________
Expiration date: ______________________________________________________________________
Date spike sample prepared ______________________________________________________________________
Signature of field personnel ______________________________________________________________________
FIGURE 14.7 Field sample spike preparation log.

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• How pH was checked on the preserved sample and the value of the measured pH; if addi-
tional preservative was used to obtain the correct pH, how many extra milliliters were
added, and how was the blank prepared with the additional preservative
• Sequential order of the samples taken; each sample should be accompanied by a sequence
number and a field identification number
• If duplicate samples are taken, properly identified as FD1 and FD2
• If split samples are taken, correctly identified as FS1 and FS2
• Information about the preparation and true value of field quality control samples
• Spiked samples marked as FSp1 and FSp2 (if duplicates are taken)
• Field measurement data (temperature, pH, etc.)
• List of purging and sampling equipment used
• Documentation for monitoring wells:
– Well-casing composition and diameter
– Depth of water table and well
– Total volume of water purged
– Calculation used for volume purged
– Date and time well was purged
– Measurements to monitor stabilization of wells: purging should continue until
measurements (temperature, pH, conductivity) are stable. If no measurements are
taken, at least five well volumes must be purged before sample collection can begin
• Documentation for surface waters (depth at which samples were taken)
• Documentation for wastewater effluent:
– If composite samples were taken, beginning and ending times of composition
– Duration of compositing
– Volume of subsamples
• Documentation for soil and sediments (depth at which samples were taken)
• Documentation for drum sampling:
– Type of drum and description of contents
– If stratified, layer(s) sampled
• How samples are transported to the laboratory (packing, cooling, separated, etc.)
• Sample transmittal form (typically, chain-of-custody form), which must include the fol-
lowing information:
– Site name and address
– Date and time of sample collection
– Name of sampler
– Complete identification of samples, such as field identification number, number of
samples, date and time sample collected, requested analysis, preservation, and
comments about the sample
Failure to fill out these records properly could result in data invalidation.
14.8 FIELD QUALITY CONTROL

The quality of data resulting from sampling activities is measured by quality control (QC) proce-
dures. The goals of QA/QC in sample collection are to prove the validity of data derived from field
measurements and to prevent improper sampling techniques and inadequacies in sample preserva-
tion, identification, and transportation. Field QA/QC is described in Section 13.5.
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14.8.1 GENERAL REQUIREMENTS OF FIELD QA/QC PROGRAM

• Availability of field standard operating procedure (FSOP)
• Documentation of calibration and maintenance of field instruments and equipment
• Qualification and training of field personnel
• QC check criteria
• Validation of field measurements
• Written statement about packing and transfer of collected samples to laboratory
14.8.2 FIELD QUALITY CONTROL CHECK CRITERIA

14.8.2.1 Equipment Blanks
Equipment blanks are used to detect contamination from sampling equipment. This blank is pre-
pared in the field before sampling begins by using the precleaned equipment and filling the proper
sample container with analyte-free water. Preservation and documentation of the blank are the same
as for collected samples. If equipment is cleaned on site, then additional equipment blanks should
be collected for each equipment group. Each sample matrix should be accompanied by separate
equipment blanks.
14.8.2.2 Field Blanks

Field blanks are collected at the end of sample collection by filling the sample container with ana-
lyte-free water and are preserved and documented in the same way as the collected samples.
14.8.2.3 Trip Blanks

Trip blanks are collected to verify contaminations that may occur during sample collection and trans-
portation (improperly cleaned sample containers, contaminated reagents, contamination during
transportation, etc.). Trip blanks are blanks of analyte-free water prepared in the laboratory and
transported to the field. They remain unopened during the sampling event and are transported back
to the laboratory with the collected samples. Trip blanks should be properly labeled and documented!
14.8.2.4 Duplicates
Duplicates are samples collected at the same time from the same source. During one sample collection
event, at least one sample or 10% of the collected samples (whichever is greater) should be duplicated.
14.8.2.5 Split Samples

Split samples are replicas of the same sample that are given to two independent laboratories
for analysis.
14.8.2.6 Field Spiked Samples

Spiked samples are used to measure the performance of the complete analytical system, including in-
terference from the sample matrix. Spiked samples are environmental samples with the addition of
known concentrations of the analyte of interest. Field preparation, preservation, and documentation
should be the same as for the collected samples. Selection of spiked and split samples may be dic-
tated by the requirements of the site, a previsit evaluation, or on-site inspection.
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14.8.2.7 Validation of Field Measurements

Field measurements are validated through precision (based on duplicate samples) and accuracy
(based on measurement of the known value of a QC sample). Calculations of precision and accuracy
are discussed in Section 13.9.
14.9 SAMPLE COLLECTION FROM DIFFERENT MATRICES

14.9.1 GROUNDWATER SAMPLING
Groundwater, the base flow of all perennial flows, accounts for over 90% of the world’s freshwater
resources. Groundwater is the primary source of drinking water; about 50% of the U.S. population
uses groundwater. In many instances of groundwater contamination, the ability to predict how the
contaminant plume will behave in the future can only be done on the basis of an extensive drilling
and sampling program. The most frequently used approach in groundwater quality monitoring is to
collect and analyze water samples from monitoring wells. The purpose of a monitoring well is to de-
termine hydrogeologic properties, provide a facility for collecting water samples, and monitor the
movement of the contamination plume. Critical factors include the number and location of monitor-
ing wells and the depth at which samples are taken.
14.9.1.1 Well Purging Prior to Sampling

• Prior to sampling, an adequate amount of stagnant well water must be removed so that the
collected water sample will be representative of groundwater conditions.
• For most wells, removing three to five well volumes is adequate, or until the values of tem-
perature, pH, and conductivity measurements of the water are stabilized.
• Wells should be sampled within 6 h of purging.
14.9.1.2 Water Level Measurement

Water levels are measured by using electronic tape or chalked tape, among other techniques. When
electrical devices are used, a light or ammeter indicates a closed circuit when the probe touches
the water. Depth markers are commonly attached to the cable by the manufacturer at about 5-ft
(1.5-m) intervals. When using a steel tape, a lead weight is attached to the bottom. The lower end
of the tape is wiped dry and coated with carpenter’s chalk before measurement. The tape is dropped
into the well, and after withdrawal the wetted line of the tape can be read on the chalked section.
The reading is subtracted from the foot mark held at the measuring point; the difference is the
water level depth.
14.9.1.3 Sampling Technique Using a Bailer

The bailer is the most common sampling equipment used for collecting samples from groundwater.
Bailers are constructed in a wide variety of diameters and in a wide variety of materials. They are
easy to transport, easy to clean, and inexpensive. The disadvantage of the bailer is that atmospheric
oxygen may be introduced when the sample is transferred into the sampling bottle. Select the mate-
rial for the bailer that is convenient for collecting metal-analysis samples (stainless steel, plastic, or
Teflon). As with all sampling equipment, the bailer must be scrupulously clean. The bailer is illus-
trated in Figure 14.8. Wear latex rubber gloves to avoid sample contamination.
1. Lower the bailer slowly into the well. As the bailer moves slowly down through the water
in the well, the check valve remains open, allowing the water to pass through the bailer.
2. At the desired depth, stop lowering the bailer.
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Line for lowering and lifting
Rigid Teflon tubing
Glass-marble ball-and-seat valve
Teflon extruded rod
FIGURE 14.8 Teflon bailer. The top of the bailer is open and the bottom contains a sample ball-and-seat check
valve arrangement. As the bailer moves down through the water in the well, the check valve remains open, and
the water passes through the bailer. As the bailer is lifted, the weight of water inside the bailer causes the ball
valve to seat, thus trapping the sample inside.
3. As the bailer is lifted, the weight of the water inside the bailer will close the valve, trap-
ping the sample inside.
4. When the bailer reaches the surface, the sample is transported to the sampling bottle. (As
mentioned previously, the preferred material of sample containers for metals analysis is
polyethylene.)
5. Remove the cap from the bottle and rinse the bottle with the sample. Do not rinse the bot-
tle if it is a prepreserved container!
6. Fill the bottle with the sample, but do not fill to the top. Leave space for the addition of
preservative and mixing.
7. With a pipet or a premeasured dropper, add 3 ml of 1+1 HNO3 or 1.5 ml concentrated
HNO3 per liter of sample to take the sample pH to less than 2. If prepreserved bottles are
used, do not add acid!
8. Mix sample well; pour a small amount of sample into a small, disposable container; and
check the pH with narrow range pH paper. If the pH is not less than 2, add more preser-
vative until the desired pH is achieved.
9. Record the volume used, the concentration of the preservative, and the measured pH of the
preserved sample in the field notebook and on the sample label.
10. The corresponding equipment blank should contain the same amount of preservative as the
sample. Samples with additional preservative should have a separate blank with the same
amount of acid as in the sample.
11. Samples for hexavalent chromium (Cr6+) do not need preservative. Carefully select the
sampling container. Do not use prepreserved sampling bottle! Complete sample label and
transfer to the laboratory as soon as possible.
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12. If the analysis request is for suspended and dissolved metal determination, the sample
should be filtered prior to preservation and treated as discussed in Section 14.5.2.
13. Quality control requirements are dependent on the project plan. Field quality control
checks are listed in Section 14.8.2.
14. Affix the sample labels, fill out the chain-of-custody form, and record all sampling data in
the field notebook, as discussed in Section 14.7.1.
14.9.2 DRINKING WATER SAMPLING

14.9.2.1 Sampling Potable Well Water
When sampling drinking water from residential, private potable wells, the wells must be purged as
described in Section 14.9.1. If the capacity of the pressure tank is not known, purge the well for about
15 to 20 min. After purging, reduce the flow to approximately 500 ml/min. Take samples as discussed
in Section 14.9.1.3, steps 5 to 14.
14.9.2.2 Sampling from Distribution System

Samples should be collected in areas free from excessive dust, rain, snow, or other sources of con-
tamination. If samples are collected from faucets, the faucet should be clean and free from possible
contamination. The faucet should also be flushed thoroughly, generally 2 to 3 min, but sometimes a
longer flush is needed, such as when sampling to test for lead pollution. After flushing the water, ad-
just the flow so that it does not splash against the walls of bathtubs, sinks, or other surfaces. Then col-
lect samples as discussed in Section 14.9.1.3, steps 6 to 15.
14.9.3 SAMPLING SURFACE WATERS

Selection of sample sites depends on the nature of the sampling project, type of samples, and whether
the sites are permanent monitoring stations established by the Surface Water Improvement and
Management (SWIM) program.
14.9.3.1 General Rules in Surface Water Sampling

• When gathering samples from a powerboat, samples must be taken from the bow, away
and upwind from the outboard gasoline engine.
• Both water and sediment samples should be collected from downstream to upstream.
• When water and sediment samples are taken from the same area, water samples must be
collected first.
• Care should be taken not to disturb sediment when taking water samples.
• Do not take samples at or near dams, piers, or bridges, because the unnatural water flow
may disturb the representativeness of the sample.
14.9.3.2 Grab Samples

Grab samples are taken by using unpreserved containers.
1. Submerge the container in the water.

2. Invert the bottle so that the neck is upright and pointing to the water flow. Fill the bottle
and return it to the surface.
3. Pour out a small quantity of the sample to leave space for adding preservative and mixing.
4. Preserve samples and follow activities as discussed in Section 14.9.
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5. Another grab sampling method is to use a pole-mounted flask and follow steps 1 to 4
above. This kind of equipment must be constructed of material that does not interfere with
the sampled parameters. (If the pole is copper, of course, the sample would not be accept-
able for copper testing.) When using a pole sampler, samples can be taken from a bridge,
a boat, or from the shore.
6. Composite samples are taken when a given depth interval is desired for the sample. Care
should be taken that all subsamples are of equal volume (Section 14.1.4).
7. A peristaltic pump may also used to take grab or composite samples.
14.9.3.3 Samples Taken at Different Depths in Same Sample Location

Samples are taken just below the surface, at mid-depth, and just above the bottom. For this kind of sam-
pling, a depth-specific sampler, such as the Kemmerer sampler, a pump, or a bailer may be used. Each
kind of sampling equipment should be selected based on the proper material for the parameter of inter-
est. For example, for metal testing, the equipment should be made of stainless steel, plastic, or Teflon.
The Kemmerer sampler is illustrated in Figure 14.9. Collect and preserve samples as in Section 14.9.3.
14.9.3.4 Sediment Samples

Sediment samples are usually taken as a part of surface water samples. Equipment used for sediment
sampling varies according to sample location, water depth, sediment grain size, and water velocity.
The most common sampling equipment types are scoops, corers, Eckman sampler (for sand, silt, and
mud sediments), and the Peterson and Ponar sampler (for hard, rocky sediments). The Eckman bot-
tom grab sampler is illustrated in Figure 14.10.
14.9.4 SAMPLING WASTE WATER

Requirements for the analyzed parameters from both municipal and industrial waste waters are
regulated by the National Pollutant Discharge Elimination System (NPDES) permit program.
FIGURE 14.9 Modified Kemmerer sampler.

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FIGURE 14.10 Eckman bottom-grab sampler.
These permits specify the types and amounts of pollutants that may be discharged and are in-
tended to ensure that the effluent content remains within the limits of the relevant groundwater or
surfacewater standard. Sampling locations should be described in the permit or the project plan.
14.9.4.1 General Criteria for Collecting Representative Samples

• Sampling time should not exceed 15 min.
• Samples must be taken where wastewater flow is properly mixed.
• The most representative sample from effluent should be taken downstream from the
wastewater stream before it enters the disposal site (surface water, wetland, deep-well in-
jection, etc.)
• The best point for sampling from influents is from the turbulent flow where the sample is
well mixed.
• When taking a sample, the container should be inverted and submerged below the waste-
stream surface and filled. Do not use prepreserved sample bottles! Follow up with activi-
ties discussed in Section 14.4.3, steps 6 to 14.
• When collecting composite samples, the compositing interval and duration as well the
sampling point should be described in the project plan. Use of automatic samplers
is practical.
14.9.5 SAMPLING AGRICULTURAL DISCHARGES

Agricultural discharges can be categorized into three types:
1. Concentrated animal waste or manure

2. Runoff from an agricultural watershed
3. Irrigation return flow
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The frequency and location of sampling, the number of samples, and the required parameters
must be followed as stated in the discharge permit.
14.9.6 COLLECTING DOMESTIC SLUDGE

All samples for sludge classification should be representative and taken after final sludge treatment
but before disposal. The preferred container for metals analysis is plastic, and the sample is preserved
with HNO3.
14.9.7 COLLECTING SOIL SAMPLES

All samples for soil analysis should be representative of the area to be sampled. If the area where the
sample is taken shows natural disturbances (e.g., dead vegetation or discoloration), the sample must
be accompanied by a sample from a uncontaminated area. For metals analysis, the preferred con-
tainer is plastic. The material of the sampling equipment is dictated by the need to avoid contami-
nating the selected analyte group in the sample.
14.9.7.1 General Rules for Soil Sampling

1. Wear natural latex rubber gloves.
2. Select the appropriate sampling devices.
3. Select the appropriate sample container.
4. Take the soil sample, mix well in a stainless steel plate, and transfer into the sample con-
tainer with minimal headspace.
5. Clean sample container exterior if necessary, and label it.
6. Fill out chain-of-custody form and field notebook.
7. Place the sample container into a plastic bag.
8. When samples are collected from a large area, composition of soil samples is recom-
mended to reduce the number of samples. Composition of the samples should be handled
in stainless steel or glass containers. The origin and sample size of each subsample must
be documented in the field notebook.
14.9.7.2 Surface Soil Sampling

Before taking the sample, remove dirt, leaves, and grass from the soil surface, and take the sample
with a stainless steel spoon or scoop.
14.9.7.3 Shallow Subsurface Soil Sampling

Dig a hole with a stainless steel shovel, bucket, or auger to the desired depth. To avoid the collapse
of the hole, insert a rigid PVC support into the hole, and after sampling, remove the support.
14.9.7.4 Deep Subsurface Soil Sampling

The sample is taken from a hole more than 15 ft below the surface. Various types of sampling
equipment are available for this kind of sample collection. For rocks and hard soils, the head of the
sampling device has a small diamond bit to cut through the hard surfaces as the drilling rod is ro-
tated.
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14.9.8 SAMPLING HAZARDOUS WASTES

To ensure representative sample collection, a sampling plan should be available to determine the cor-
rect number of samples taken with the appropriate frequency. Hazardous material samples can be gas,
liquid, solid, paste, sludge, or some combination. Therefore, methods and equipment vary according
to sample makeup. Reaction of the sample with sunlight or temperature should also be taken into ac-
count. Be sure that the sampling equipment and sample containers do not react with the waste sample!
The most common sampler is the colivasa, designed to sample free-flowing liquids from drums,
open tanks, and pits, among other sources. It consists of a metal, glass, or plastic tube equipped with
an end closure that can be opened and closed. Open and lower the colivasa into the waste and let the
tube fill. Lock the stopper and withdraw from the waste. Wipe the exterior with a disposable cloth
and transfer the sample to the sample container. The colivasa sampler is illustrated in Figure 14.11.
Another type of liquid sampler is the weighted bottle. It is a glass or plastic bottle with a sinker,
stopper, and a line that is used to lower, raise, and open the bottle. Lower the bottle into the sample,
let it fill (when bubbling stops, the bottle is filled), raise, and use the bottle itself as a sample container.
The dipper, a beaker on the end of a long pole, is similar to the weighted bottle. Dippers are use-
ful for sampling liquids and free-flowing slurries.
xxxxx Locking
Slopper rod PVC
Pipe PVC
152 cm (5' -0")
SAMPLING POSITION CLOSE POSITION
FIGURE 14.11 Composite liquid waste sampler, colivasa, used in sampling free-flowing liquids and slurries
from drums, shallow open tanks, pits, and so on. Ensure that the sampler is clean. Open and lower into the
sample material and let the tube fill. Lock the stopper and withdraw sampler. Wipe the exterior with a dispos-
able cloth.
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FIGURE 14.12 Sampling trier (left), used in sticky

solids and loose soils, is a tube cut in half lengthwise
with a sharpened top that allows cutting into the sample
material. Insert clean trier into the sample, cut the core,
remove with concave side up, and transfer sample to
container. Thief sampler (right), used in any bulk mate-
rial, is especially useful in sampling grain-like material.
80 - 100 cm
It consists of two slotted concentric tubes, usually made
80 - 100 cm
of brass or stainless steel. Insert clean, closed thief into
sample. Wiggle sampler to let material enter the slots.
Close, withdraw, and remove inner tube; transfer sample
to the sample container.
The trier, used for sampling sticky solids and loosened soils, is a tube with a sharpened tip. Insert
the trier into the waste, cut the core, remove with concave side up, and transfer the sample into the
sample container. The sampling trier is illustrated in Figure 14.12.
For bulk material, the best sampler is the sampling thief, and for hard and packed solids, a con-
venient sampler is the auger. Scoops and shovels are also useful for sampling granular or powdery
materials.
The material of the sample container should be chosen so that it will not react with the sample.
The container should be resistant to leakage and breakage and the appropriate size for the sample.
Wide-mouth plastic containers with tight, screw-type lids are desirable if the sample is not used for
organic analyte determination. After the sample is taken, clean the container exterior, label properly,
and place in a plastic bag for transport to the laboratory. When the nature of the hazardous material
is known, a safety label should also be affixed to the sample container. Common safety labels are
shown in Figure 14.13.
Corrosive Poison Flammable
Cancer
Warning
Water Reactive Air Reactive Radioactive Cancer Warning
Explosive Oxidizer
FIGURE 14.13 Safety labels.

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14.9.8.1 Safety Concerns

The person collecting hazardous waste samples must realize that these samples are hazardous mate-
rials and should be handled with extreme care! Therefore, the collector should wear protective
gloves, face aspirator, and special safety clothing, shoes, and hazard hat. After sampling, clothes,
shoes, and hat must be removed. Each time after sampling, the sample collector must wash hands and
exposed portions of the body; in some cases, a full shower is appropriate. A fire extinguisher should
be available if the material is flammable and the sampling site is small. If a large quantity of flam-
mable material is at the sampling site, a fire truck should be present. When sampling flammable ma-
terials with a high vapor pressure or low flashpoint, all equipment should be grounded and all sources
of ignition should be prohibited. As a general rule, avoid eating and smoking during sampling.
14.9.9 SAMPLING FISH TISSUES

Fish tissues are usually analyzed for metals and organic pollutants. Equipment used for sampling
should be scrupulously cleaned and decontaminated properly. First, wash equipment with laboratory
detergent, rinse with deionized water, isopropylalcohol, and finally, analyte-free water. The dried
equipment should be stored in aluminum foil until use. The captured fish is placed in wet ice in a
cooler. In the laboratory, weigh and prepare the tissue. The fillet should not be skinned. The fish tis-
sue should be wrapped in aluminum foil and kept in wet ice for 24 h, or frozen for longer storage.
14.9.10 COLLECTING AIR SAMPLES

Dust, silica, and other suspended particles in the air are measured by gravimetry. The filter in the cas-
sette should be weighted before and after sampling for accurate mass determination of deposited par-
ticles. For metals analysis, the metal dusts deposited on the filter must be acid digested and analyzed
via atomic absorption spectrometry or inductively coupled plasma spectrometry.
The primary concern of the sampler must be directed to the collection of representative samples
and the homogeneity of the air mixtures employed to calibrate both the collection and the analytical
systems. The concentration of the contaminant at a specific location is influenced by the source of
contaminant, airflow direction and velocity (due to wind or thermal gradients), density of the con-
taminants, intensity of sunlight, time of day, and presence of obstructions, such as trees, buildings,
and machinery (which produce turbulence and humidity).
14.9.10.1 Sampling and Storage of Particles

Many sampling methods are available, and the method selected depends on the purpose of the sam-
pling. For example, for chemical analysis, a Hi-Vol sampler is employed. All parts of the airstream
must be sampled and properly weighted so that the entire stream is represented. The size and type of
the filter paper are usually dictated by the instrument and sample site. Particles can react with filter
paper, evaporate, and sublimate, depending on the nature of the sample. The analyst must always con-
sider the method prior to the sampling. For many purposes, particulate samples tend to keep well for
a long period of time.
Site selection is important in all types of air sampling, but especially for particles because they
are much less uniformly dispersed in ambient air as well as in process equipment. Particles of all sizes
are continually emitted into the atmosphere. Large particles fall rapidly, while smaller sizes fall more
slowly. The height of the source, wind velocity and turbulence, and particle size distribution will de-
termine how fast the particles settle out. Very small particles (Attken nuclei) tend to become attached
to larger particles. Aerosol samples are dispersions of any material in the solid or liquid phase in a
gas stream or the atmosphere. Particles can be categorized into the following size groupings:
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Settleable particles, larger than 30 µm in diameter

Suspended particles, smaller than 30 µm in diameter
Condensation or Attken nuclei, 0.01 to 0.1 µm in diameter
Agglomerates, several small particles attracted by a large particle or attracted to each other
Fine particles, particles less than 2.5 µm in diameter
Coarse particles, particles greater than 2.5 µm in diameter
14.9.10.2 Isokinetic Sampling of Particles

The momentum of a particle is mass × velocity. Particles of different sizes are displaced by different
amounts. Isokinetic sampling refers to taking a sample under conditions in which there is no change
in momentum. This is accomplished by using a thin-walled tube aligned with the stream flow and
drawing the sample into it and at the same linear velocity as the stream flow at that point. Particles
of all sizes can thus be collected efficiently.
14.9.10.3 General Rules for Particulate Sampling

A 24-h sampling has become a standard practice. General rules for particulate sampling follow:
• Take the sample at the point of major interest.

• Do not place the sampler directly downwind from a major point source.
• Place the sampler about 1.45 m above ground level.
• Locate downwind from major obstacles at a distance of about ten times their height.
• Take several samples at different locations in the area of interest.
• Sample during the time of day of greatest interest, or take a 24-h sampling.
The objective is to collect a sample that is representative of the material emitted. The specific
points of sampling are generally determined by discussion with plant engineers or others who un-
derstand the process or the source of emission. A site visit is generally required for final selection.
Particulate sampling should be carried out with probes inserted in the duct at each end of the points-
of-flow measurement. Care must be exercised to ensure that particles may be vaporized. If the am-
bient temperature is too low, water or other vapors form mist that will collect with the solids and plug
up the filter, leading to bad results.
For each sample, the following data must be attached:
• Date and time of collection

• Sample location
• Sample flow rate
• Sample pressure
• Sample temperature
• Dew point
• Plant operating condition
• Sampler’s name
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Sample Preparation
15 for Metals Analysis

Samples containing particulate or organic material generally require pretreatment before analysis.
15.1.1 SAMPLE PRETREATMENT FOR TOTAL METALS

Colorless, transparent samples (primarily drinking water) containing a turbidity of less than 1 NTU
(nephelometric turbidity unit), and single-phase samples can be analyzed directly via atomic absorp-
tion spectroscopy or inductively coupled plasma spectroscopy for total metals without digestion. For
further verification or to determine changes in existing matrices, compare digested and undigested
samples to ensure comparable results. Digest all other samples before determination of total metals.
Take care not to introduce metals into samples during preliminary treatment. During pretreat-
ment, avoid contact with rubber, metal base paints, cigarette smoke, paper tissues, and all metal prod-
ucts, including those made of stainless steel, galvanized metal, and brass. Conventional fume hoods
can contribute significantly to sample contamination, particularly during acid digestion in open con-
tainers. Plastic pipet tips are often contaminated with copper, iron, zinc, and cadmium. Before use,
soak pipets in 2N HCl or HNO3 for several days and rinse with deionized (DI) water. Check reagent-
grade acids used for preservation, extraction, and digestion for purity. If excessive metal concentra-
tions are found, purify the acids by distillation or use ultra-pure acids. Carry blanks through all di-
gestion and filtration steps and apply necessary corrections to the results.
15.1.2 SAMPLE PRETREATMENT FOR DISSOLVED METALS

To analyze for dissolved metals, filter the sample (as in Section 15.1.4), acidify the filtrate, and ana-
lyze directly.
15.1.3 SAMPLE PRETREATMENT FOR SUSPENDED METALS

To determine suspended metals, filter the sample, digest the filter and the material on it, and analyze.
15.1.4 PRELIMINARY FILTRATION OF SAMPLES

If dissolved or suspended metals are to be determined, filter the sample at the time of collection. Use
a preconditioned, plastic, vacuum (or pressure) device equipped with a filter support made of plastic
or TFE. The filter should have the following characteristics: prewashed, ungridded, 0.45-µm mem-
brane, and made of polycarbonate or cellulose acetate. Before use, filter a blank consisting of reagent
water to ensure freedom from contamination. Precondition the filter and filter device by rinsing with
50-ml of DI water. If the filter blank contains significant metal concentrations, soak membrane filters
227
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in approximately 0.5N HCl or 1+1 HNO3 and rinse with water before use. If the filter is to be digested
for suspended metals, record the sample volume filtered, and analyze a digested filter as a blank.
Before filtering, centrifuge highly turbid samples in acid-washed TFE or a high-density plastic tube
to reduce loading on filters. Stirred-pressure filter units foul less readily than vacuum filters. Filter at
a pressure of 70 to 130 kPa (kiloPascal; 1 atm (atmosphere) = 100 kPa).
After filtration, acidify filtrate to pH 2 with HNO3 concentrate and analyze directly. If a precipi-
tate forms on acidification, digest acidified filtrate before analysis. Retain filter and digest it for di-
rect determination of suspended metals.
15.1.5 SAMPLE PRETREATMENT FOR ACID-EXTRACTABLE METALS

To determine acid-extractable metals, extract metals as indicated below and analyze extract.
Extractable metals are lightly absorbed on particulate material. Because some sample digestion may
be unavoidable, use rigidly controlled conditions to obtain meaningful and reproducible results.
Maintain constant sample volume and contact time. Express results as extractable metals and spec-
ify extraction procedure.
At the time of collection, acidify the entire sample with 5 ml of HNO3 concentrate per liter of
sample. Extract metals as follows:
1. Mix sample well.
2. Transfer 100 ml of the sample to a beaker or flask.
3. Add 5 ml of 1+1 HCl.
4. Heat for 15 min over a steam bath.
5. Filter through a membrane filter, adjust filtrate volume to 100 ml with laboratory-pure
water, and analyze.
15.2 DIGESTION PROCEDURES FOR METALS

15.2.1 INTRODUCTION
To reduce interference by organic matter and to convert metal associated with particulate to a form
(usually a free metal) that can be determined by AAS or ICP, use one of the digestion techniques pre-
sented below. Use the least rigorous digestion method required to provide complete and consistent
recovery compatible with the analytical method and the metal being analyzed.
HNO3 will digest most samples adequately. Nitrate is an acceptable matrix for both FAAS and
GrAAS. Some samples may required the addition of perchloric, hydrochloric, or sulfuric acid for
complete digestion. These acids may interfere in the analysis of some metals and all provide a poor
matrix for GrAA analysis. Confirm metal recovery for each digestion and analytical procedure used.
Table 15.1 lists the acids used in conjunction with HNO3. As a general rule:
• HNO3 alone is adequate for clean samples or easily oxidized materials.

• HNO3–H2SO4 or HNO3–HCl digestion is adequate for readily oxidizable organic matter.
• HNO3–HClO4 or HNO3–HClO4–HF digestion is necessary for difficult-to-oxidize organic
matter or minerals.
Report the digestion technique used. Because acid digestion techniques do not normally achieve
total digestion, the microwave digestion procedure may be used as an alternate. The microwave
method is a closed-vessel procedure, and thus typically provides improved precision when compared
with the hot-plate technique. Suggested sample volumes for digesting are presented in Table 15.2.
Larger samples require additional acid.
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Sample Preparation for Metals Analysis 229
TABLE 15.1
Acids Used in Conjunction with HNO3 for Sample Preparation
Acid Recommended For May Be Helpful for Not Recommended for

HCl — Sb, Ru, Sn Th, Pb —
H2SO4 Ti — As, Pb, Ba
HClO4 — Organic materials —
HF — Siliceous materials —
TABLE 15.2
Suggested Sample Volumes for Digestion
Estimated Metal Concentration (mg/l) Sample Volume (ml)
<1 1000
1–10 100
10–100 10
100–1000 1
15.2.2 NITRIC ACID DIGESTION

1. Transfer a suitable volume (50 to 100 ml) of well-mixed sample into a 125-ml flask or
beaker.
2. Add 5 ml of HNO3 concentrate and a few boiling chips or glass beads. Bring to a slow boil
and evaporate on a hot plate to the lowest volume (10–20 ml) before precipitation occurs.
3. Continue heating and adding acid until digestion is complete, as indicated by a light-col-
ored, clear solution. Do not let sample dry during digestion.
4. Wash down flask or beaker walls with DI water and filter, if necessary. Transfer filtrate to
a 100-ml volumetric flask. Cool and dilute to the mark, and mix thoroughly.
Alternatively, take a larger sample volume using the procedure for concentration.
15.2.3 NITRIC ACID–HYDROCHLORIC ACID DIGESTION

1. Transfer a suitable volume of the well-mixed, acid-preserved sample appropriate for the
expected metal concentrations to a flask or beaker.
2. Add 3 ml of HNO3 concentrate. Heat on a hot plate and evaporate to less than 5 ml, mak-
ing certain that the sample does not boil and is not allowed to dry.
3. Cool and add another 5 ml of acid. Cover container with a watch glass and return to a hot
plate. Increase temperature of the hot plate so that a gentle reflux action occurs.
4. Continue heating, adding additional acid as necessary until digestion is complete, indi-
cated by a light-colored and clear digestate.
5. Evaporate to less than 5 ml and cool. Add 10 ml of 1+1 HCl and 15 ml of DI water per
100-ml total volume. Heat for an additional 15 min to dissolve any precipitate or residue.
6. Cool, wash down beaker walls and watch glass with DI water, and filter to remove insol-
uble material that could clog the nebulizer. Alternatively, centrifuge or let settle overnight.
7. Adjust to a predetermined volume based on expected metal concentrations.
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15.2.4 NITRIC ACID–SULFURIC ACID DIGESTION

1. Transfer a suitable volume of the well-mixed, acid-preserved sample into a flask or beaker.
2. If sample is not already acidified, acidify to methylorange endpoint with H2SO4 concen-
trate and add 5 ml of HNO3 concentrate and a few boiling chips or glass beads.
3. Bring to slow boil on a hot plate and evaporate to 15 to 20 ml.
4. Add 5 ml of HNO3 concentrate and 10 ml of H2SO4. Evaporate on a hot plate until dense
white fumes of SO3 begin to form. If the solution does not clear, add 10 ml of HNO3 con-
centrate and repeat evaporation until fumes of SO3 begin to form. Heat to remove all HNO3
before continuing treatment. All HNO3 will be removed when the solution is clear and no
brownish fumes are evident. Do not let sample dry during digestion.
5. Cool and dilute to about 50 ml with DI water. Heat to almost boiling to dissolve slowly
soluble salts. Filter if necessary.
6. Complete procedure by transferring filtrate into a volumetric flask and dilute to the mark.
Mix thoroughly.
15.2.5 NITRIC ACID–PERCHLORIC ACID DIGESTION

1. Mix sample and transfer a suitable volume into a flask or beaker.
2. If sample is not already acidified, acidify to methylorange endpoint with HNO3 concen-
trate, add an additional 5 ml of HNO3 concentrate and a few boiling chips or glass beads,
and evaporate on a hot plate to 15 to 20 ml.
3. Add 10 ml each of HNO3 concentrate and HClO4, cooling flask or beaker between addi-
tions. Evaporate gently on a hot plate until dense white fumes of HClO4 begin to appear.
4. If solution is not clear, cover container with a watch glass and keep solution at boiling tem-
perature (but no higher), boiling until it clears.
If Pb is to be determined in the presence of high amounts of sulfate (e.g., determination of Pb in

power-plant fly ash in samples), dissolve PbSO4 precipitate as follows:
1. Add 50 ml of ammonium acetate solution to flask or beaker in which digestion was car-
ried out, and heat to incipient boiling. Rotate container occasionally to wet all interior sur-
faces and dissolve any deposited residue.
2. Using a preconditioning plastic filtering device with either vacuum or pressure and contain-
ing a filter support of plastic or TFE, filter the sample through a prewashed ungridded 0.45-
mm membrane filter as described in Section 15.1.4.
3. Transfer filtrate to a 100-ml volumetric flask, cool, dilute to the mark, mix thoroughly, and
set aside for determination of Pb.
Caution: Heated mixtures of perchloric acid (HClO4) and organic matter may violently explode.
Avoid this hazard by taking the following precautions:
• Do not add HClO4 to a hot solution containing organic matter. (Always pretreat samples
containing organic matter with HNO3 before adding HClO4!)
• Avoid repeated fuming with HClO4 in ordinary hoods. (For routine operations, use a water
pump attached to a glass fume eradicator. Stainless-steel fume hoods with adequate water
wash-down facilities are available commercially and are acceptable when using HClO4.)
• Never let samples being digested with HClO4 evaporate to dryness.
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15.2.6 NITRIC ACID–PERCHLORIC ACID–HYDROFLUORIC ACID DIGESTION
Caution: See precautions for using HClO4 in Section 15.2.5. Handle with extreme care and provide
adequate ventilation, especially for the heated solution. Avoid all contact with exposed skin. Seek
medical attention for hydrofluoric acid burns.
1. Mix sample and transfer a suitable volume into a 250-ml TFE beaker.
2. Add a few boiling chips and bring to a slow boil. Evaporate to 15 to 20 ml.
3. Add 12 ml of HNO3 concentrate and evaporate to near dryness. Repeat HNO3 addition and
evaporation.
4. Cool solution and add 20 ml of HClO4 and 1 ml of HF, and boil until solution is clear and
white fumes of HClO4 have appeared.
5. Cool, add about 50 ml of DI water, filter, and proceed as directed in Section 15.4.2, step 4.
15.2.7 DRY ASHING

Dry ashing is helpful if large amounts of organic matter are present. Dry ashing yields highly vari-
able precision and bias depending on the sample type and metal analyte.
1. Mix sample and transfer a suitable volume into a platinum or high-silica-glass evaporat-
ing dish (Vycor, manufactured by Corning Glass Works, or equivalent).
2. Evaporate to dryness over a steam bath.
3. Transfer dish to a muffle furnace and heat sample to a white ash. If volatile elements are
to be determined, keep temperature at 400 to 450°C.
4. If only Na is to be determined, create the ash sample at a temperature up to 600°C.
5. Dissolve ash in a minimum quantity of HNO3 concentrate and warm water. Filter diluted
sample and adjust to a known volume, preferably so that the final HNO3 concentration is
about 1%.
6. Use a portion of this solution for metal determination.
15.2.8 MICROWAVE-ASSISTED DIGESTION
Caution: This method is designed for microwave digestion of waters only. It is not intended for the
digestion of solids, in which high concentrations of organic compounds may result in high pressure
and possibly unsafe conditions.
15.2.8.1 Requirements for Microwave Unit

Use a microwave unit with programmable power (minimum 545 W) to within ±10 W of required
power, with a corrosion-resistant, well-ventilated cavity, and with all electronics protected against
corrosion for safe operation. Use a unit with a rotating turntable with a minimum speed of 3 rpm to
ensure homogeneous distribution of microwave radiation. Only laboratory-grade microwave equip-
ment and closed digestion containers with pressure relief that are specifically designed for hot acid
should be used.
Vessels should be constructed of perfluoroalkoxy (PFA) Teflon capable of withstanding pres-
sures of at least 760±70 kPa (±110 psi) and capable of controlled pressure relief at the manufacturer’s
maximum pressure rating. Acid wash all digestion vessels and rinse with reagent water. When using
a new PFA Teflon vessel or when changing between high- and low-concentration samples, clean by
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leaching with hot 1+1 HCl for a minimum of 2 h and then with hot 1+1 HNO3 for a minimum of 2 h,
rinse with reagent water, and dry in a clean environment.
15.2.8.2 Procedure
The following procedure is based on heating acidified samples in two stages where the first stage is
to reach 160±4°C in 10 min, and the second stage is to permit a slow rise to 165–170°C during the
second 10 min. A verified program that meets this temperature-time profile is 545 W for 10 min fol-
lowed by 344 W for 10 min using five single-wall PFA Teflon digestion vessels. The usable number
of vessels is determined by vessel design and power output.
1. Weigh entire digestion vessel assembly to 0.1 g before use and record (A).
2. Accurately transfer 45 ml of well-shaken sample into the digestion vessel.
3. Pipet 5 ml of HNO3 concentrate into each vessel. Make sure that pressure-cap relief disks
are inserted according to manufacturer’s directions. Tighten caps to manufacturer’s spec-
ification.
4. Weigh each capped vessel to the nearest 0.1 g (B).
5. Evenly distribute the appropriate number of vessels in the carousel.
6. Treat sample blanks, known additions, and duplicates in the same manner as samples.
7. When fewer samples than the appropriate number are digested, fill the remaining vessels
with 45 ml of reagent water and 5 ml of HNO3 concentrate to obtain the full complement
of vessels for the particular program in use.
8. Place carousel in microwave and set it carefully on the turntable. Program microwave unit
to heat samples to 160±4°C in 10 min; for the second stage, permit a slow rise to 165 to
170°C for 10 min. Start microwave generator, making sure that the turntable is turning and
that the exhaust fan is on.
9. Upon completion of the microwave program, let vessels cool for at least 5 min in the unit
before removal. Samples may then be cooled further outside the unit by removing the
carousel and letting them cool on a bench or in a water bath. When cooled to room tem-
perature, weigh (to 0.1 g) each vessel and record weight (C).
10. If the net weight of sample plus acid decreased by more than 10%, discard sample.
11. Complete sample preparation by carefully uncapping and venting each vessel in a fume
hood. Transfer to acid-cleaned, noncontaminating plastic bottles. If the digested sample
contains particulate, centrifuge at 2000 to 3000 rpm for 10 min and then filter or let settle
overnight.
15.2.8.3 Calculation
Dilution correction: Multiply results by 50/45, or 1.11, to account for the dilution caused by
the addition of 5 ml of acid to a 45-ml sample.
Discarding of sample: To determine if the net weight of the sample plus acid decreased by
more than 10% during the digestion process, use the following calculation:
[(B − A) − (C − A)]/(B − A) × 100 > 10% (15.1)

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15.2.8.4 Quality Control (QC)

Including a QC sample in each loaded carousel is recommended. Prepare samples in batches, in-
cluding preparation blanks, sample duplicates, and predigested known additions. Determine size of
batch and frequency of QC samples according to the analytical method and laboratory practice. The
power of the microwave unit and batch size may prevent including one or more QC samples in each
carousel. Do not group QC samples together but distribute them throughout the various carousels to
render the best monitoring of digestion.
15.3 ACID DIGESTION FOR TOTAL AND DISSOLVED METALS
15.3.1 INTRODUCTION
This procedure is used to prepare surfacewater and groundwater samples for analysis by flame
atomic absorption spectroscopy (FAAS) or by inductively coupled plasma spectroscopy (ICP),
for the following metals: Al, Sb, As*, Ba, Be, Cd, Ca, Cr, Co, CI, Fe, Pb, Mg, Mn, Ni, K, Se*,
Ag, Na, Ta, V, and Zn (* = ICP only). Note that this digestion procedure may not be vigorous
enough to destroy some metal complexes. Total metal samples must be acidified at the time of
collection with HNO3. For dissolved metals, all samples must be filtered through a 0.45-µm fil-
ter and the filtrate acidified with HNO3 (see Section 15.1). (For discussion of sample preserva-
tion, see Section 14.4.)
15.3.2 PROCEDURE
1. Measure 100-ml aliquot of well-mixed sample into a beaker. (To avoid metal contamina-
tion, the cleaned beaker should be rinsed with 1+1 HNO3.)
2. Add 2 ml of concentrated HNO3 and 5 ml of concentrated HCl. Cover with a ribbed watch
glass, and heat in a steam bath or on a hot plate at 90 to 95°C until the volume is reduced
to 15 to 20 ml. Do not boil! Antimony (Sb) is easily lost by volatilization from HCl media.
3. Remove from hot plate and allow to cool.
4. Wash down the beaker walls and watch glass with DI water. If necessary (i.e., when
suspended material appears), filter or centrifuge the sample to remove suspended ma-
terials. Caution: The filter and filtration apparatus should be washed with 1+1 HNO3 be-
fore filtration.
5. Adjust the final volume to 100 ml with DI water.
Note: As and Se determination from this digestate are suitable for the ICP technique only.
15.3.3 QUALITY CONTROL (QC)

Together with the samples, at a frequency of 5% or one per analytical batch, the following should be
digested as part of the quality control process:
1. 100 ml of analyte-free water, called the preparation blank (prep blank)

2. 100 ml of calibration verification standard (CVS), called laboratory control sample (LCS)
3. Spiked sample (spiked sample may be duplicated instead of a sample duplicate)
4. One sample duplicate
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15.4 ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS

FOR TOTAL METALS BY FLAME ATOMIC ABSORPTION
SPECTROMETRY (FAAS) AND INDUCTIVELY COUPLED
PLASMA (ICP) ANALYZER
15.4.1 INTRODUCTION
This digestion procedure is used to determine total metals in the preparation of aqueous samples,
EPTOX and mobility-procedure (TCLP) extracts, and wastes that contain suspended solids for FAAS
and ICP analysis. Samples may be analyzed for the following parameters: Al, As, Ba, Be, Cd, Ca, Cr,
Co, Co, Fe, Pb, Mg, Mn, Mo, Ni, K, Se, Na, Tl, V, and Zn. This procedure is not suitable for samples
that will be analyzed by GrAAS because HCl can cause interference during furnace atomization.
Collection and preservation of samples are discussed in Section 14.4.
15.4.2 PROCEDURE
1. Transfer 100-ml representative aliquot of well-mixed sample into a beaker. (The cleaned
beaker should be rinsed with 1+1 HNO3 to avoid contamination.)
2. Add 3 ml of concentrated HNO3.
3. Cover the beaker with a ribbed watch glass and place on a hot plate. Heat slowly, until it
evaporates to about 5 ml. Do not boil sample! Make certain that no portion of the bottom
of the beaker is allowed to dry.
4. Cool and add 3 ml of concentrated HNO3.
5. Recover the beaker with the watch glass and return to the hot plate.
6. Increase the temperature of the hot plate so that a gentle reflux action occurs.
7. Continue heating, adding additional acid if necessary, until the sample is clear and light in
color.
8. Evaporate until the volume is about 3 ml. Do not dry sample! If a sample is allowed to dry
or burn, discard and redigest.
9. Cool, add about 10 ml of 1+1 HCl and warm up for 15 min to dissolve all of the precipi-
tate and residue.
10. Wash down the beaker wall and watch glass with DI water, and filter or centrifuge, if nec-
essary, to remove silicates and other insoluble material that could clog the nebulizer. This
step may cause contamination, unless the filter and filtering apparatus are thoroughly
cleaned and rinsed with diluted HNO3.
11. Adjust the final volume to 100 ml with DI water.

As a QC requirement, the substances listed in Section 15.3.3 should be digested together with the an-
alytical samples at a frequency of 5% or one per analytical batch (as described in Section 15.3.3).
15.5 ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS

FOR TOTAL METALS BY GRAPHITE FURNACE
SPECTROSCOPY (GrAAS)
15.5.1 INTRODUCTION
This digestion procedure is used for the preparation of aqueous samples, EPTOX and mobility-pro-
cedure (TCLP) extracts, and wastes that contain suspended solids for analysis by GrAAS for the
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following metals: Be, Cd, Cr, Co, Pb, Mo, Tl, and V. (Digestion and GrAAS analysis for As, Se, and
Ag are different. The digestion procedure for As and Se is described in Section 15.8, and for Ag in
Section 15.9.) Aqueous samples must be acidified to a pH of less than 2 with HNO3, while nonaque-
ous samples should be refrigerated as soon as possible.
15.5.2 PROCEDURE
1. Transfer 100-ml aliquot from well-mixed sample into a beaker. (The cleaned beaker
should be rinsed with 1+1 HNO3 to avoid contamination.) Cover the beaker with a ribbed
watch glass.
2. Heat on a hot plate (do not boil!) until the sample evaporates to a volume of 5 ml (do not dry!).
3. Cool and add another 3 ml of concentrated HNO3.
4. Continue heating, and add additional acid if necessary, until the sample is clear, and light
in color.
5. Evaporate to about 3 ml of volume. Do not dry!
6. Add 10 ml of DI water and heat for about 10 to 15 min.
7. Wash down the walls of the beaker and the watch glass with DI water and filter if
necessary.
8. Complete to 100 ml of volume with DI water.

See Section 15.3.3.
15.6 SAMPLE PREPARATION FOR ARSENIC AND SELENIUM

DETERMINATION BY GRAPHITE FURNACE
SPECTROSCOPY (GrAAS)
15.6.1 INTRODUCTION
This method is used in the determination of As and Se in groundwater, wastes, extracts, and soils.
Aqueous samples must be acidified to a pH of less than 2 with HNO3 at the time of collection.
Nonaqueous samples must be refrigerated and analyzed as soon as possible. Furnace parameters
should be employed by following the method described in Chapter 9. The calibration curve should
be calculated every hour when continuous analysis is employed.
15.6.2 PROCEDURE FOR AQUEOUS SAMPLES

1. Transfer 100 ml of well-mixed sample into a beaker. (The cleaned beaker should be rinsed
with 1+1 HNO3 to avoid contamination.)
2. Add 2 ml of 30% H2O2 and sufficiently concentrated HNO3 to result in an acid concentra-
tion of 1% (v/v).
3. Heat for 1 h at 95°C or until the volume is slightly less than 50 ml.
4. Cool and bring back the volume to 50 ml with DI water.
5. Pipet 5 ml of this digested solution into a 10-ml volumetric flask.
6. Add 1 ml of 1% nickel nitrate (Ni(NO3)2) solution, and dilute to 10 ml of volume with DI
water. The sample is now ready to inject into the furnace.
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15.6.3 PROCEDURE FOR SOLID SAMPLES

Solid samples digestion for arsenic and selenium analysis is the same as described in Section 15.10.

See Section 15.3.3.
15.7 SAMPLE PREPARATION FOR SILVER DETERMINATION

The digested samples are analyzed by the flame atomic absorption method and approved for deter-
mination of silver in wastes, extracts, soils, and ground waters.
1. Transfer a representative aliquot of well-mixed sample to a beaker, add 3 ml concentrated

HNO3, and cover the beaker with a watch glass.
2. Place the beaker on a hot plate and cautiously evaporate to near dryness, taking care that
the sample does not boil. Do not bake!
3. Cool the beaker and add another 3-ml portion of concentrated HNO3 and cover again with
the watch glass and return to the hot plate. Increase the temperature, so that a gentle reflux
action occurs. Note: If the sample contains thiosulfates, this step may result in splatter of
the sample as the sample approaches dryness (as with some photographic types of waste
samples).
4. Continue heating and adding additional acids until the digestate is light in color and does
not change in appearance with further refluxing.
5. Evaporate to dryness and cool.
6. Add a small quantity of HNO3, so that the final dilution contains 0.5% (v/v) acid, and
warm to dissolve any precipitate.
7. Wash down the wall of the beaker and the watch glass with DI water, filter if necessary,
and dilute to volume. (Volume depends on the expected concentration of the metal.)
15.8 SAMPLE PREPARATION FOR ANTIMONY DETERMINATION

For antimony (Sb) determination, the recommended sample preparation method is soft digestion, as
discussed in Section 15.1. The addition of HCl to the digestate prevents furnace analysis!
15.9 SAMPLE PREPARATION FOR MERCURY DETERMINATION

(COLD-VAPOR TECHNIQUE)
15.9.1 PREPARATION OF AQUEOUS SAMPLES

1. Transfer 100 ml (or an aliquot diluted to 100 ml) to a 300-ml BOD bottle.
2. Add 5 ml of 0.5 nitrogen sulfuric acid (H2SO4) and 2.5 ml of concentrated HNO3, mixing
after each addition.
3. Add 15 ml of 5% potassium permanganate (KMnO4) solution to each bottle. Shake and
add additional portions of KMnO4 until the purple color is persistent for at least 15 min.
(Be sure that the same amount of permanganate is added to the accompanied standards and
blanks!)
4. Add 8 ml of 5% potassium persulfate (K2S2O8).
5. Heat for 2 h in a water bath maintained at 95°C.
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6. Cool and add 6 ml of sodium chloride–hydroxylamine sulfate or hydroxylamine

hydrochloride (12 g per 100 ml of DI water) to reduce excess KMnO 4.
7. After a delay of at least 30 sec, add 5 ml of stannous sulfate or stannous chloride suspen-
sion (10 g per 100 ml of 0.5N H2SO4 by stirring continuously), and immediately attach to
the aeration apparatus and analyze.
8. Blanks, calibration standards, QC check standards, and spiked samples must be treated the
same way.
15.9.2 PREPARATION OF SOLID AND SEMISOLID SAMPLES

1. Weigh three 0.2-g portions of untreated sample and place in the bottom of a 300-ml BOD
bottle.
2. Add 5 ml of DI water and 5 ml of aqua regia (3:1 HCl and HNO3).
3. Heat for 2 min in a water bath at 95°C.
4. Cool and add 50 ml of DI water and 15 ml of 5% KMnO4 solution.
5. Mix thoroughly and place on the water bath at 95°C for 30 min.
6. Cool and add 6 ml of 12% of hydroxylamine hydrochloride or sodium chloride-hydroxy-
lamine sulfate solution to reduce excess KMnO4. Caution: Add this material under a fume
hood because chlorine (Cl2) could evolve!
7. Add 55 ml of DI water and 5 ml of 10% stannous chloride or stannous sulfate solution,
immediately attach to the aeration apparatus, and analyze.
8. Calibration standards and QC checks are treated in the same way.
9. For calculations to report on the dry base, the percent moisture content of the sample
should be determined as described in Appendix I.
15.10 ACID DIGESTION OF SEDIMENTS, SLUDGES, AND SOILS

FOR TOTAL METALS ANALYSIS
15.10.1 INTRODUCTION
This method is an acid digestion procedure used to prepare sediments, sludges, and soil samples for
analysis by FAAS, GrAAS, or ICP. Samples prepared with this method may be analyzed by ICP for
all listed metals and by FAAS or GrAAS as indicated below:
FAAS: Al, Ba, Be, Cd, Ca, Cr, Co, Cu, Fe, Pb, Mg, Mn, Mo, Ni, K, Na, Tl, V, Zn
GrAAS: As, Be, Cd, Cr, Co, Fe, Mo, Se, Tl, V
A representative (wet weight) sample of 1 to 2 g is digested in HNO3 and H2O2. The digestate is
then refluxed with either HNO3 or HCl. Diluted HCl is used as the final reflux acid for the ICP analy-
sis of As and Se, and the FAAS or ICP analysis of Al, Ba, Be, Ca, Cd, Cr, Co, Cu, Fe, Mo, Pb, Ni, K,
Na, Tl, N, and Zn. Dilute HNO3 is employed as the final dilution acid for GrAAS analysis of As, Be,
Cd, Cr, Co, Pb, Mo, Se, Tl, and V. A separate sample should be dried for a total solids determination.
All samples must be collected as discussed in Chapter 14.
15.10.2 PROCEDURE
1. Mix sample thoroughly to achieve homogeneity.
2. Weigh 1 to 2 g of sample into a beaker. (The cleaned beaker should be rinsed with 1+1
HNO3 before use to avoid contamination.)
3. Add 10 ml of 1+1 HNO3 and mix with the solid sample.
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4. Cover with a watch glass, heat to about 90 to 95°C, and reflux for 10 to 15 min without
boiling.
5. Cool and add 2 ml of DI water and 3 ml of 30% hydrogen peroxide (H2O2).
6. Put back onto the hot plate for warming until effervescence stops. (Peroxide reaction is ef-
fervescent.)
7. Continue the addition of 30% H2O2 in 1-ml portions, and warm until effervescence stops
or until the general sample appearance is unchanged. Do not add more than a total of 10
ml of 30% H2O2.
15.10.2.1 Sample Preparation for Flame AA and ICP Techniques, Including

ICP Analysis of As and Se
1. Add 5 ml of concentrated HCl and 10 ml of DI water and reflux for 10 to 15 min without
boiling.
2. Cool and dilute to 100 ml with reagent water.
3. Due to particulate in the digestate that may clog the nebulizer, filter through with Whatman
No. 41 filter paper, and fill up the filtrate to 100 ml with DI water. Alternatively, centrifuge
at 2000 to 3000 rpm for 10 min. The final concentration of the diluted sample is 5% (v/v)
HNO3 and 5% (v/v) HCl.
15.10.2.2 Sample Preparation for GrAAS Technique

Use this method if the sample is prepared for GrAAS technique to determine As, Be, Cd, Cr, Co, Pb,
Mo, Se, Tl, and V.
1. Same as step 1 for FAAS technique (Section 15.10.2.1), but instead of HCl, add HNO3.
2. Cover the sample with a ribbed watch glass and continue heating the acid–peroxide di-
gestate until the volume has been reduced to approximately 5 ml.
3. After cooling, dilute to 100 ml with reagent water.
4. Particulate in the digestate should then be removed by filtration or centrifugation or by set-
tling as mentioned above. Final concentration of the diluted sample is 5% (v/v) HNO3.
15.10.2.3 Calculation of Results and Reporting for Solid Samples

For solid samples, the values are reported as dry-weight milligrams per kilogram or micrograms per
kilogram. Therefore, the dry solid percentage of the sample must be provided. Dry weight is calcu-
lated as discussed in Appendix I.

1. For each group of samples processed, preparation blanks (reagent water plus reagents)
should be carried through the entire sample preparation and analytical process. These
blanks are useful in determining whether samples are contaminated.
2. Duplicate samples should be processed on a routine basis and are used to determine pre-
cision. The sample load will dictate frequency, but 20% is recommended.
3. Spiked samples or standard reference materials must be employed to determine accuracy.
A spiked sample should be included with each group of samples processed and whenever
a new sample matrix is analyzed.
4. The concentration of all calibration standards should be verified against a QC check sam-
ple obtained from an outside source.
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15.11 DISSOLUTION PROCEDURE FOR OILS,

GREASES, AND WAXES
This method is used for the preparation of samples containing oils, greases, or waxes for analysis via
AAS or ICP for the following metals: Sb, Be, Cd, Cr, Cu, Fe, Mn, Ni, and V. This method is a sol-
vent-dissolution procedure, not a digestion. The procedure can be very useful in the analysis of crude
oil, but is less effective with spent or used oil with a high amount of particulate material; most par-
ticulate material is not dissolved; therefore, the analysis is not a “total metal” determination. Because
particulate material is expected to contain the highest percentage of metal, oil analysis using this
method will not provide an adequate estimate of total metal concentration.
15.11.1 PROCEDURE
A representative sample is dissolved in an appropriate solvent (e.g., xylene or methyl-isobutyl-ke-
tone). Organometallic standards are prepared using the same solvent, and the samples and standards
are analyzed via AAS or ICP.

1. All samples must be collected using a sampling plan that addresses considerations dis-
cussed in Chapter 14.
2. Samples should be stored in an undiluted state at room temperature.
3. Samples should be processed and analyzed as soon as possible.
15.11.3 PROCEDURE
1. Weigh 2-g representative sample of the waste or extract. Separate and weigh the phases if
more than one phase is present.
2. Weigh an aliquot of the organic phase and dilute it in the appropriate solvent. Warming fa-
cilitates the subsampling of crude type oils, greases, and wax-type wastes. Xylene is usu-
ally the preferred solvent for long-chain hydrocarbons and for most analyses performed
via ICP. Long-chain hydrocarbons require a minimum 1:10 dilution, and lighter oils re-
quire 1:5 dilutions if low detection limits are required.
3. All metals must be analyzed by the standard addition method (Section 7.7.1.1).
4. Organometallic standards are prepared by using the same solvent. Diluted samples and di-
luted organometallic standards are unstable. Once standards and samples are diluted, they
should be analyzed as soon as possible.
Organometallic standards are available from Conostan Division, Conoco Specialty Products, Inc.,
P.O. Box 1267, Ponca City, OK 74601, and U.S. Department of Commerce, National Bureau of
Standards, Washington, D.C. 20234.
15.12 SAMPLE PREPARATION FOR HEXAVALENT CHROMIUM

(CHELATION/EXTRACTION)
This method is approved for determining the concentration of dissolved hexavalent chromium in
EPTOX-characteristic extracts and groundwaters. It may also be applicable to certain domestic and
industrial wastes, provided that no interfering substances are present (high concentrations of other
metals may interfere). The procedure is applicable in the range of 0.1 to 25 µg/l Cr6+ concentrations.
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To retard the chemical activity of Cr6+, the samples and extracts should be stored at 4°C until sample
preparation. Chelation and extraction should be carried out as soon as possible.
15.12.1 REAGENTS
15.12.1.1 Potassium Dichromate Standard Solution I
1 ml = 100 µg Cr
Use 0.2829 g of pure dried potassium dichromate (K2Cr2O7). Dissolve and dilute to 1 liter with ana-
lyte-free water.
15.12.1.2 Potassium Dichromate Standard Solution II
1 ml = 10 µg Cr
Use 10 ml of potassium dichromate standard solution I. Dilute to 100 ml with analyte-free water.
15.12.1.3 Potassium Dichromate Standard Solution III
1 ml = 0.10 µg Cr
Use 10 ml of potassium dichromate standard solution II. Dilute to 1 liter with analyte-free water.
15.12.1.4 Ammonium Pyrolidine Dithiocarbamate (APDC)

Dissolve 1.0 g of APDC in DI water and dilute to 100 ml. Prepare fresh daily!
15.12.1.5 Bromphenol Blue Indicator Solution

Dissolve 0.1 g of bromphenol blue in 100 ml of 50% ethanol.
15.12.1.6 Methyl Isobutyl Ketone (MIBK) Analytical Reagent Grade
15.12.1.7 Sodium Hydroxide Solution, 1M

Dissolve 40 g of sodium hydroxide (NaOH) in DI water and dilute to 1 liter. Because the reaction is
highly exothermic, the solution should be prepared with extreme care under a laboratory hood!
15.12.1.8 Sulfuric acid, 0.12M

Slowly add 6.5 ml of sulfuric acid (H2SO4) to DI water and dilute to 1 liter.
15.12.2 CHELATION AND EXTRACTION

1. Prepare a blank and a sufficient number of standards (minimum of 3) at a volume of 100 ml.
2. Pipet a volume of sample of less than 2.5 µg (maximum 100 ml) into a 200-ml volu-
metric flask. If the sample is less than 100 ml, adjust the volume to 100 ml with analyte-
free water.
3. Add two drops of bromphenol blue indicator solution to samples, blank, and standards.
4. Adjust the pH by adding drops of 1M NaOH solution until the blue color persists.
5. Add 0.12M H2SO4 until the blue color disappears. Then add 2 ml of sulfuric acid in ex-
cess. The pH in this point should be 2.4.
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6. Add 5.0 ml of APDC solution and mix. The pH should be approximately 2.8.
7. Add 10 ml of MIBK and shake vigorously for 3 min.
8. Allow the layers to separate and add DI water until the ketone layer is completely in the
neck of the flask. Determine the chromium content by aspirating the ketone layer into the
flame of an atomic absorption spectrophotometer. At the same time chelate and extract
also a calibration verification standard (CVS) and spike duplicate. (Run a spike duplicate
sample for every ten samples.)
15.13 EXTRACTION PROCEDURE (EP) TOXICITY

Extraction procedure (EP) toxicity (EPTOX test) is designed to simulate the leaching a waste under-
goes when disposed of in a sanitary landfill. In this laboratory test, a representative sample of a waste
is extracted with distilled water maintained at a pH of 5, using acetic acid. The extract obtained from
the EP is then analyzed to determine if any of the thresholds established for the eight elements (ar-
senic, barium, cadmium, chromium, lead, mercury, selenium, and silver), four pesticides (Endrin,
Lindane, Methoxychlor, and Toxaphene), and two herbicides (2,4,5-trichloropnenoxypropionix acid
and 2,4-dichlorophenoxyacetic acid) have been exceeded. If the extract contains any one of the above
substances in an amount equal to or exceeding the levels specified in 40 CFR, 261.24, the waste pos-
sesses the characteristic of EP toxicity and is a hazardous waste. Maximum concentration of con-
taminants for EP toxicity characteristics are discussed in Section 4.7.4 and are listed in Table 4.5. The
EP method is applicable to liquid, solid, and multiphase samples.

All samples must be collected using a sampling plan that addresses the considerations discussed in
Chapter 14. Preservatives must not be added to samples. Samples can be refrigerated if refrigeration
will not affect the integrity of the sample.
15.13.3 APPARATUS AND MATERIALS

15.13.3.1 Extractor
The extractor must provide sufficient agitation to the mixture to prevent stratification of the sample
and extraction fluid and ensure that all sample surfaces are continuously brought into contact with
the well-mixed extraction fluid. An example of a suitable extractor for this method is shown in
Figure 15.1. Extractors are available from Associated Designs & Manufacturing Co., Alexandria, VA;
Glas-Col Apparatus Co., Terre Haute, IN; Millipore, Bedford, MA; and Rexnard, Milwaukee, WI.
15.13.3.2 pH Meter
The pH meter must be accurate to 0.05 pH units with temperature compensation.
15.13.3.3 Filter Holder

The filter holder should be capable of supporting a 0.45-µm filter membrane and withstanding the
pressure needed to accomplish separation. Suitable filter holders range from simple vacuum units to
relatively complex systems that can exert up to 5.3 kg/cm3 (75 psi) of pressure. The filter holders used
depend on the properties of the mixture to be filtered.
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15.13.3.4 Filter Membrane

Filter membranes suitable for conducting the required filtration are fabricated from a material that is
not physically changed by the waste material to be filtered and does not absorb or leach the chemi-
cals from the waste. In cases of doubt about physical effects on the filter, contact the filter manufac-
turer to determine if the membrane or the prefilter is adversely affected by the particular waste. If no
information is available, submerge the filter in the waste’s liquid phase; a filter that undergoes visi-
ble physical change after 48 h (e.g., if it curls, dissolves, shrinks, or swells) is unsuitable for use.
To test the filter for absorption or leaching, take the following steps:
1. Prepare a standard solution of the chemical species of interest.

2. Determine the concentration of the chemical in the standard.
3. Filter the standard and reanalyze. If the concentration of the filtrate differs from the orig-
inal standard, the filter membrane leaches or absorbs one or more of the chemical species
and it is not usable for this test method.
15.13.4 REAGENTS
15.13.4.1 Acetic Acid (0.5N)
Add 57 ml of concentrated glacial acetic acid (17.5N) to 1000 ml of laboratory water and dilute to
2 liters. The glacial acetic acid should be of high purity and monitored for impurities.
15.13.5 PROCEDURE
15.13.5.1 Liquid or Multiphase Samples
1. Weigh filter membrane and prefilter to ±0.01 g. Handle membrane and prefilters with
blunt, curved-tip forceps or vacuum tweezers, or by applying suction with a pipet.
2. Assemble filter holder, membranes, and prefilters following the manufacturer’s instruc-
tions. Place the 0.45-µm membranes on the support screen and add prefilters in ascending
order of pore size. Do not prewet filter membrane.
3. Weigh out a representative subsample of the waste (100 g minimum).
4. Allow slurries to stand to permit the solid phase to settle. Wastes that settle slowly may be
centrifuged prior to filtration.
5. Wet the filter with a small portion of the liquid phase of the sample or with the extraction
mixture. Transfer the remaining material to the filter holder and apply vacuum or gentle
pressure (10–15 psi) until all liquid passes through the filter. Stop filtration when air or
pressurizing gas moves through the membrane. If this point is not reached under vacuum
or gentle pressure, slowly increase the pressure in 10-psi increments to 75 psi. Halt filtra-
tion when liquid flow stops. This liquid will constitute part or all of the extract. The liquid
should be refrigerated until analysis.
6. Remove the solid phase and filter and, while not allowing them to dry, weigh to 0.01 g.
Wet weight of the residue (g) = B − A (15.2)
where
B = weight of the solid phase and filter (g).
A = weight of the filters (g).
7. If the solid content is less than 0.5% of the waste, discard the solid. The extract is prepared
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and analyzed. Determine the exact percentage of solids by drying the filter and residue at
80°C and then calculate as follows:
% solids = (C − A) / D × 100 (15.3)
where
C = dry weight of the filter and residue.
A = weight of the filters.
D = initial weight of the waste.
Do not extract solid material that has been dried at 80°C!

8. If the sample contains less than 0.5% solids, use the wet weight of the solid phase ob-
tained in step 6 to calculate the amount of liquid and acid employed for extraction. If the
waste does not contain free liquids, 100 g of the material should be subjected to the ex-
traction procedure.
9. Place the appropriate amount of material into the extractor (see step 8).
10. Add reagent-grade water at 16 times the weight of material. Begin agitation and measure
the pH of the solution in the extractor. If the pH is more than 5.0, the pH of the solution
should be decreased to 5.0±0.2 by adding 0.5N acetic acid. If the pH is less than 5.0, no
acetic acid should be added. Monitor the pH during extraction and, if the pH rises above
5.2, more 0.5N acetic acid should be added to bring the pH down to 5.0±0.2. The pH of
the solution should be checked and adjusted at 15-, 30-, and 60-min intervals. This ad-
justment procedure should be continued for at least 6 h. However, in no event should the
aggregate amount of acid added to the solution exceed 4 ml of acid per gram of solid. The
mixture should be agitated for 24 h and maintained at 22 to 40°C (68–104°F) during this
time.
11. If at the end of the extraction period the pH of the solution is not below 5.2 pH and the
maximum amount of acid has not been added, adjust the pH of the solution to 5.0±0.2 and
continue the extraction for an additional 4 h, during which the pH should be checked at
1-h intervals.
12. At the end of the extraction period, calculate the amount of the reagent-grade water added
to the extractor:
V = [(20)(W) − 16(W)] − Ac (15.4)
where
V = ml of reagent-grade water added.
W = weight of solid extracted.
Ac = ml of 0.5N acetic acid added during extraction.
13. Allow the extracted material to stand to permit the solid phase to settle. Wastes that are
slow to settle may be centrifuged prior to filtration.
14. Set up filtration apparatus as in step 2. Wet the filter with the extraction mixture. Transfer
material to the filter holder and apply vacuum or gentle pressure (10–15 psi) until all liq-
uid passes through the filter. Stop filtration when air or pressurizing gas moves through the
membrane. Slowly increase the pressure in 10-psi increments to 75 psi. Halt filtration
when liquid flow stops.
15. Combine filtrate with the remaining liquid from step 5 or the waste itself if it contains less
than 0.5% of solid (step 7).
16. The extract is prepared and analyzed. If the extract includes two phases, concentration of
L1572_C15 5/23/02 1:43 PM Page 244
contaminants is determined by using a simple weighted average. For example, assume that
the extract contains 50 ml of oil and 1000 ml of aqueous phase. Determine the contami-
nant concentration for each phase and calculate the final concentration according to the
following formula:
[(50)(concentrate in oil)] + [(1000)(concentrate in aqueous phase)]/1050 (15.5)
15.13.5.2 Solid Samples

If a representative sample of the waste contains more than 0.5% of solids, the solid phase of the sam-
ple is ground to pass through a 0.5-mm sieve and extracted with reagent-grade water maintained at a
pH of 5.0±0.2, with acetic acid. Follow the procedure in Section 15.3.5.1, steps 8 through 16.

All QC measures described in Chapter 13 should be followed. Employ a minimum of one blank per
sample batch to determine if contamination effects are occurring.
15.14 EXTRACTION PROCEDURE FOR OILY WASTES

This method is used to determine the mobile metal concentration in oily wastes. The method is ap-
plicable to EPA-defined separator sludges, rag oil emulsions, and other oil wastes derived from pe-
troleum refining.
1. The sample is separated into solid and liquid components by filtration.

2. The solid phase is placed in a Soxhlet extractor charged with tetrahydrofuran (THF) and
extracted.
3. When the THF is recovered, the extractor is then charged with toluene and the sample is
re-extracted.
4. The EP extraction method (Section 15.13) is run on the dry solid residue.
5. The original liquid, combined extracts, and EP leachate are analyzed for the EP toxicity
metals (As, Ba, Cd, Cr, Pb, Hg, Se, and Ag).
15.14.2 INTERFERENCES
Matrix interferences should be extracted from the sample. The extent of these interferences varies
considerably from waste to waste, depending on the nature and diversity of the particular refinery
waste being analyzed.
15.14.3 APPARATUS AND MATERIALS

Soxhlet extraction apparatus (see Appendix K)
Vacuum pump or other source of vacuum
Buchner funnel 12
Electric heating mantle
Paper extraction thimble
Filter paper
Evaporating flask, 250 ml
Apparatus and materials listed in Section 15.3.3
L1572_C15 5/23/02 1:43 PM Page 245
15.14.4 REAGENTS
15.14.4.1 Tetrahydrofurane, ACS Reagent Grade
15.14.4.2 Toluene, ACS Reagent Grade
15.14.4.3 Acetic Acid, 0.5N

Preparation is discussed in Section 15.13.4.1.
15.14.5 SAMPLING
Samples must be collected in glass containers having a total volume of at least 150 ml. No solid ma-
terial should interfere with sealing the sample container. Sampling devices should be wiped clean
with paper towels or absorbent cloth, rinsed with a small amount of hexane followed by acetone
rinse, and dried between samples. Alternatively, samples can be taken with disposable sampling de-
vices in beakers.
15.14.6 PROCEDURE
1. Separate the sample (minimum of 100 g) into solid and liquid components using the fil-
tration steps in Section 15.13.5.1, steps 1 through 6.
2. Determine the quantity of liquid (milliliters) and the concentration of the species of inter-
est in the liquid phase (milligrams per liter) using appropriate analytical methods.
3. Place the solid phase into a Soxhlet extractor, charge the concentration flask with 300 ml
of tetrahydrofuran, and extract for 3 h.
4. Remove the flask containing tetrahydrofuran and replace it with one containing toluene.
5. Extract the solid for a second time for 3 h with toluene.
6. Combine the tetrahydrofurane and the toluene extracts.
7. Determine the quantity of liquid (milliliters) and the concentration of the species of inter-
est in the combined extract (milligrams per liter).
8. Take the solid material remaining in the Soxhlet thimble and dry it at 100°C for 30 min.
9. Run the EP procedure (Section 15.13) on the dried solid.
10. Calculate the mobile metal concentration in milligrams per liter using the following
formula:
1000 × (Q1 + Q2 + Q3) / (L2 − L1) (15.6)
where
Q1 = amount of metal in initial liquid phase of sample (amount of liquid × concentration
of metal in milligrams; see step 2).
Q2 = amount of metal in combined organic extracts of sample (mg) (see step 7).
Q3 = amount of metal in EP extract of solid (amount of extract × concentration of metal in
milligrams; see step 9).
L1 = amount of initial liquid in milligrams (see step 2).
L2 = amount of liquid in extraction procedure (20 × weight of dried solid).
L1572_C15 5/23/02 1:43 PM Page 246

Laboratory duplicates should be analyzed to validate analytical precision. QC samples should be car-
ried through all stages of sample preparation and measurement and analyzed to validate the sensitiv-
ity and accuracy of the analysis.
15.15 DOCUMENTATION DURING SAMPLE PREPARATION

All numerical data relating to preparation processes and that require further calculations should be
briefly documented (volume or weight of the samples used for preparation, dilution factors, concen-
trations, reagent preparations, pH checks, etc.). Each container carrying the pretreated sample should
be properly identified with sample ID, date of preparation, and all pertinent information (volume,
weight, dilution, concentration, etc.) related to the preparation procedure. A sample preparation log
sheet is illustrated in Table 15.3.
15.16 DISPOSAL OF SAMPLES, DIGESTATES, EXTRACTS,

AND OTHER WASTES
Samples and pretreated samples in the form of extracts and digestates should be stored properly until
the end of recommended holding times. Refrigerators and separate storage areas must be designated
for this purpose. Regular water samples may be disposed of into the sewer system, with the excep-
tion of hazardous wastes. Hazardous laboratory wastes are stored in special containers until collected
and transported by a professional waste disposal company. Such vessels should be marked clearly ac-
cording to the nature of the waste, such as “acid wastes,” “organic solvents,” “mercury waste,” and
so on. Disposal of samples and treated products should be documented as shown in Table 15.4.
L1572_C15
TABLE 15.3
5/23/02
Sample Preparation Log Sheet (per Analyte Group)

1:43 PM
Sample Size
Sample I.D. Method No. Method No. Date Sample Date Sample Final Volume
Matrix Test for Signature
Number Analysis Prep. Rec’d. Prep. (ml)
(ml) (g)
Page 247
Sample Preparation for Metals Analysis

247
L1572_C15 5/23/02 1:43 PM Page 248
TABLE 15.4
Disposal Log Form for Digestates and Extracts
Date Sample Mode of

Sample ID Date of dispo Sign
rec prep prep dispo
Sample ID = sample identification number; rec = received; prep = prepared; dispo = disposed; Sign = signature of logger.
Mode of preparation:
D = digested; E = extracted; Dist = distilled.
Mode of disposal: Storage:

Ac.W. = acid waste container Designated area
B.W. = basic waste container Designated area
Org.S. = organic solvent container “Flammable” cabinet
Hg.W. = mercury waste container Designated area
CN = cyanide waste container Designated area
L1572_C16 5/23/02 1:58 PM Page 249
Converting Raw Data into

16 Reportable Form
Raw data are generated by the analytical process, which includes QC checks. Reportable data or
final results are generated from raw data by mathematical or statistical calculations. Final results may
be produced by direct readings from the instrument or calculations based on readings or instrument
output. Before starting calculations, make sure that all readings or outputs are correct and the selected
formulas used in calculations are appropriate. Formulas and calculations should be recorded in the
laboratory notebook or on the work sheet. In all records, calculations are entered in ink and mistakes
are never erased; just cross through the error with a single line, and date and sign. Generation of raw
data and all related calculations and complete record keeping are the responsibility of the analyst.
16.1 RESPONSIBILITIES OF THE ANALYST

The following list contains the duties of the analyst from the selection of proper samples for a par-
ticular analysis through analytical performance, including QC checks, documentation, calculations,
recognition and correction of problems, and giving the accurate, defendable result.
• Analytical work should be planned and organized so that laboratory time is used effi-
ciently.
• The analyst should be familiar with the test method described in the laboratory SOP (stan-
dard operating procedure).
• If samples require pretreatment (drying, digestion, extraction, etc.), start as soon as possi-
ble because pretreatments are usually time-consuming procedures. If sample preparation
is the duty of another laboratory section, the analyst must be certain that sample prepara-
tion was correct; collect all information required to calculate the final results (volume or
weight of the sample used for treatment, final volume after treatment, moisture of soil, di-
lution or concentration, etc.). Carefully select the accompanying pretreated QC check
samples (duplicates, spiked samples, laboratory control samples, preparation blank,
equipment blanks, trip blanks, etc.).
• When samples are stored in a refrigerator, remove the bottles prior to starting the analysis
to allow samples to warm up to room temperature.
• Carefully check sample label for identification and scrupulously select samples according
to proper bottle type and preservation.
• Collect and check stocks, standards, QC check standards, and respective preparation dates.
When the expiration date indicates, discard these solutions and prepare new ones, and be
sure that all related preparation log forms are completed. When reagents are stored in a re-
frigerator, allow them to warm up to room temperature before use.
• Standardize solution when applicable, and document on the designated form.
• Collect the appropriate work form, according to test and matrix, and prepare for starting.
249
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• Collect the necessary glassware and check cleanliness and appropriate cleaning procedure.
Improperly cleaned glassware will ruin the test. Mark glassware as needed and organize.
• Switch instrument on and let it warm up.
• Prepare calibration standards by selecting the proper range as indicated by the analytical
method, and document each step properly.
• Prepare calibration curve and verify according to initial and continuing calibration crite-
ria as detailed in Sections 6.6 and 13.6. Be sure that calibration curve and linear regression
calculations are documented, and keep records (manual forms, strip charts, or tabular
printouts).
• When a previously approved calibration curve is available, perform a continuing calibra-
tion check, and indicate acceptance or rejection of the calibration curve. Upon acceptance
of the existing curve, sample analysis may begin. Upon rejection of the existing curve, dis-
card the former calibration and prepare a fresh one.
• Measure the precision and accuracy of the analytical performance by required QC checks
as described in the analytical methodology and laboratory SOP. When the QC data are not
acceptable, take corrective action and solve the problem. Never report results with a doubt-
ful QC check!
• If the analyte of interest shows a higher value than the concentration of the highest cali-
bration standard, dilute the sample for an accurate reading. The dilution technique and
proper calculation of the final value should be documented on the working paper or in the
laboratory notebook.
• Turbidity, color, or other interferences should be corrected according to the analytical
methodology.
• Run the analysis by following the approved method and incorporate all required
QC checks.
• The analyst should be knowledgeable enough to recognize problems, initiate and conduct
corrective actions, and keep all documentation related to the analysis clean and in order to
be ready for inspection at any time.
• The analyst should be able to protect and defend all raw data as well as reported results.
• At the end of the analysis, switch the instrument off; collect analytical wastes in desig-
nated containers (if applicable); collect dirty glassware; and transfer stocks, standards,
reagents, and samples to appropriate storage areas or to designated refrigerators.
• Collect all documentation, calculate results and QC checks, plot the accuracy and pre-
cision data on QC charts, and transfer figures to the tabulated summary log form. In the
case of deviation from the confidence limits, the analyst should identify the cause of the
failure and correct it, or report to the laboratory supervisor and QA (quality assurance)
manager for further assistance. All sample data determined at the time the “out-of-con-
trol” condition occurred must be labeled as “suspect data” and reanalyzed after the prob-
lem is resolved.
• If all QC data agree with the analytical values, the analyst transfers the result to the ana-
lytical report summary log paper or enters it into the computer. Collect all documentation
to be prepared for further questions or checking.
16.2 CALCULATIONS FOR FINAL VALUES

Raw data produced during the analytical process should be converted to appropriate measurement
units in reportable, final results. By using the appropriate formula, the analyst calculates final values
and registers them on the laboratory “result sheet” or enters them into the laboratory computer sys-
tem, to be ready for further supervision and checks.
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Converting Raw Data into Reportable Form 251
16.2.1 DILUTION AND CONCENTRATION

Dilution applied during the test should be recorded; the final result is obtained by multiplying the meas-
ured value by the dilution factor. The concentration technique used during sample preparation should
be documented; the analytical value divided by the concentration factor produces the final result.
For instance, assume that a water sample was analyzed for Pb concentration, and that the appro-
priate reading should be diluted five times. If the result of the diluted sample was 0.2 mg/l, the final
result will be 0.2 × 5 = 1.0 mg/l Pb in the sample. Next, assume that during the digestion technique,
a water sample analyzed for chromium was concentrated by a factor of 10 (original 250-ml sample
was cooked down to a 25-ml final volume) because of the low concentration of the metal in the sam-
ple. The reading of this concentrated sample was 0.06 mg/l, so the final result is 0.06/10 = 0.006 mg/l
or 6 µg/l.
16.2.2 CALCULATIONS FOR SOLIDS, MOISTURE, AND ASH

Complete and clear description of the reported analyte in appropriate measurement units is an im-
portant and critical part of generating a correct analytical result.
16.2.2.1 Solids
Determination of solids, moisture, or ash may be expressed as milligrams per liter or as percentage.
Solids as total solids (TS), suspended solids (SS), and total dissolved solids (TDS) are reported in mil-
ligrams per liter; moisture and ash results are expressed in percentages. Respective formulas follow:
mg/l solids (TS, TSS, TDS) = [(A − B) × 1000]/ml sample (16.1)
% solids (TS, TSS, TDS) = [(A − B) × 100]/ml sample (16.2)
% solids (TS, TSS, TDS) = (mg/l)/10,000 (16.3)
where A = weight of the dish and residue dried at 105°C in grams (for TS), weight of dish and residue
dried at 180°C in grams (for TDS), or weight of filter and residue dried at 105°C in grams (for TSS);
B = weight of dish in grams.
16.2.2.2 Moisture
Moisture of any solid is determined by drying a known-quantity aliquot of sample at 103 to 105°C
in a laboratory oven. After the dried sample is cooled in a desiccator, weigh it, and calculate its mois-
ture percentage by using the following formula:
% moisture = (g of solid − g of dried solid) × 100 / g of solid (16.4)
16.2.2.3 Ash
The ash content of any solid is determined by igniting a known-quantity aliquot of the well-mixed
sample at 1000°C in a muffle furnace. By knowing the weight of the original sample and the weight
of the remaining ash (ignited residue), and using the following formula, the percentage of ash con-
tent of the sample is determined and calculated:
% ash = (g of ash × 100) / g of original sample (16.5)

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16.2.2.4 Percentage Composition of Solid Sample

Determine the percentage of moisture at 105°C, as described above and using Formula 16.4. The
residue from the moisture determination is ignited at 1000°C. The difference between the weight of
the ignited residue (at 1000°C) and the dried solid (at 105°C) will give the volatile and organic com-
pounds in the sample. It is expressed also as a percentage. The remaining residue is considered as ash
(inorganic) and is calculated as a percentage.
The sum of the percentage of moisture, percentage of volatile, and percentage of ash values
should be 100%. If the sum of the calculated values is not 100%, and the checked calculations are
correct, the entire process should be repeated.
16.2.2.5 Calculating the Results of Solid Matrices

For solid matrices, the report is expressed as ppm (parts per million, or milligrams per kilogram) or
ppb (parts per billion, or micrograms per kilogram). The report should state that the reported value
is calculated on the “wet base” (also called “as is basis”) or on the “dry base.” See discussion and cal-
culations of these parameters in Appendix I.
16.2.3 CONVERSION OF MILLIGRAMS PER LITER

AND MILLIEQUIVALENTS PER LITER
16.2.3.1 Milligrams per Liter Converted to Milliequivalents per Liter

When the analyzed milligrams-per-liter value of the ion is converted to millequivalents per liter, the
first milligram value is multiplied by the factor derived from the ratio of the valence and the atomic
or formula weight:
meq/l = mg/l × (v/at. wt.) (16.6)
For example, Na has a valence of 1 and atomic weight of 22.9897; the factor is 1/22.9897 = 0.04340.
For a sulfate (e.g., SO42-), the valence is 2 and the atomic weight is 96.0636; therefore, the factor is
2/96.0636 = 0.0282.
16.2.3.2 Milliequivalents per Liter Converted to Milligrams per Liter

When the milliequivalents-per-liter value is converted to milligrams per liter, the milliequivalent
value is multiplied by a factor derived from the ratio of the atomic or formula weight divided by the
valence:
mg/l = meq/l × (at. wt./v) (16.7)
Using the same chemicals as in Section 15.2.3.1, when milliequivalents for Na are converted to mil-
ligrams, the factor will be 22.9897/1 = 22.9897. For sulfates, the factor is 96.0636/2 = 48.03.
Table 16.1 contains two-way conversion factors for milligrams and milliequivalents per liter.
16.2.4 Conversion of ppm (w/v) to mg/m3 and Vice Versa

The concentration of analytical values in air samples is generally expressed as milligrams per cubic
meter. Conversion of parts per million to milligrams per cubic meter and vice versa at standard tem-
perature and pressure (STP; 273 K and 1 atm or 760 torr) follow:
1 ppm = (mol wt/22.4) = mg/m3 (16.8)

L1572_C16 5/23/02 1:58 PM Page 253
TABLE 16.1
Two-Way Conversion Factors for mg/l to meq/l and Vice Versa
Factor Factor Factor Factor
mg/l × = meq/l × = mg/l × = meq/l × =
Cations meq/l mg/l Anions meq/l mg/l
Al3+ 0.1112 8.994 BO–2 0.02336 42.81
B3+ 0.2775 3.603 Br 0.01257 79.90
Ba2+ 0.01456 68.67 Cl– 0.02821 35.45
Ca2+ 0.04990 20.04 CO2–3 0.03333 30.00
Cr3+ 0.05770 17.33 CrO24– 0.01724 58.00
Cu2+ 0.03147 31.77 F– 0.05264 19.0
Fe2+ 0.03581 27.92 HCO–3 0.01639 61.02
Fe3+ 0.05372 18.62 HPO34+ 0.02084 47.99
H+ 0.9922 1.008 H2PO4– 0.01031 96.99
K+ 0.02558 39.10 HS 0.03024 33.07
Li+ 0.1441 6.941 HSO–3 0.01234 81.07
Mg2+ 0.08229 12.15 HSO–4 0.01030 97.07
Mn2+ 0.03640 27.47 I– 0.00788 126.9
Mn4+ 0.07281 13.73 NO–2 0.02174 46.01
Na+ 0.04350 22.29 NO–3 0.01613 62.0
NH+4 0.05544 18.04 OH– 0.05880 17.01
Pb2+ 0.009653 103.6 PO3–4 0.03159 31.66
Sr2+ 0.02283 43.81 S2– 0.05283 16.03
Zn2+ 0.03059 32.69 SO2–4 0.02082 48.03
Note: mg/l = milligrams/liter; meq/l = milliequivalent/liter; meq/l = mg/l × factor; factor = ionic charge/atomic
or formula weight (Clf = 1/35.45 = 0.02821); mg/l = meq/l × factor; factor = atomic or formula weight/ionic
charge (Clf = 35.45/1 = 35.45).
1 mg/m3 = (22.4/mol wt) = ppm (16.9)
where
22.4 = molar volume at STP = 22.4 l.
mol wt = molecular weight.
For example, 1 ppm of cyclohexane at STP = 84/22.4 = 3.75 mg/m3, and 2.93 mg/m3 of benzene at
STP = 2.93 (22.4/78) = 0.85 ppm.
16.2.4.1 Conversion of ppm to mg/m3 at Nonstandard Temperature

and Pressure
This conversion is done in two steps. First, calculate the molar volume and then calculate the reported
milligrams per cubic meter.
16.2.4.2 Determination of Molar Volume at Given Temperature

and Pressure Conditions
Molar volume can be calculated with the use of the combined gas law or the ideal gas law.
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16.2.4.2.1 Calculation Using Combined Gas Law

1. Convert temperature to Kelvin (°C + 273 = K).
2. Convert pressure to atm (1 atm = 760 torr).
3. Calculate the molar volume using the combined gas law:
P1V1/T1 = P2V2/T2 (16.10)
where
P1 = initial pressure at STP = 1 atm.
V1 = initial volume at STP = 22.4 l.
T1 = initial temperature at STP = 0°C = 273 K.
P2 = final pressure.
V2 = final volume.
T2 = final temperature.
16.2.4.2.2 Calculation Using Ideal Gas Law

1. Convert temperature to K (°C + 273 = K).
2. Convert pressure to atm if necessary (760 torr = 1 atm).
3. Calculate the molar volume by using the ideal gas law:
PV = nRT and V = nRT/P (16.11)
where
P = pressure.
V = volume.
n = number of moles of analyte.
R = ideal gas constant = 0.082 l atm/mol K.
T = temperature.
Assume that ppm and molar volume are known. Convert to milligrams per cubic meter by using the
following formula:
mg/m3 = ppm × (mol wt/molar volume) (16.12)
where ppm = mg/l and molar volume = l.
Assume that air sampling of SO3 is performed at an altitude where the temperature is 7°C and the
pressure is 725 torr. Calculate the molar volume of the compound:
T = 7°C = 7 + 273 = 280 K

P = 725 torr = 725/760 = 0.954
V = nRT/P
V = [(0.082) × (280)]/0.954
V = 24.6 l
The result of the analysis is 0.5 ppm of SO3 in the sample. Convert the ppm value to milligrams
per cubic meter:
mg/m3 = (mol wt/molar volume) × ppm

mg/m3 = (80/24.6) × 0.5 = 1.62
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16.2.5 SIGNIFICANT FIGURES

The number of significant figures refers to the number of digits reported for the value of a measured
or calculated quantity indicating the accuracy and precision of the value. The general rule is to report
only figures that are justified by the accuracy of the analytical method.
The number of significant figures is said to be the number of digits remaining when the data are
rounded. For example, when a measured value is 10.6 mg/l, the analyst should be quite certain of the
10, but may be uncertain as to whether the 0.6 should be 0.5 or 0.7, or even 0.4 or 0.8, because of the
unavoidable uncertainty in the analytical procedure. The reported value of 10.6 mg/l has three sig-
nificant figures. Rules for counting significant figures are summarized below.
16.2.5.1 Nonzero Integers

Always count as significant figures.
16.2.5.2 Leading Zeros

Leading zeros do not count as significant figures. The zeros simply indicate the position of the dec-
imal point. For example, 0.00065 has only two significant figures.
16.2.5.3 Captive Zeros

Captive zeros are located between nonzero digits and always count as significant figures. For exam-
ple, 1.034 has four significant figures.
16.2.5.4 Trailing Zeros

Trailing zeros are located at the right end of a number. They are significant only if the number con-
tains a decimal point. For example, when reporting 4600 ppb, use 4.6 ppm instead, assuming the two
significant figures are reliable.
16.2.5.5 Significant Figures in Multiplication and Division

The number of significant figures in the result is the same as the number in the least precise meas-
urement used in the calculation. For example, in 1.6 × 5.24 = 8.38, round to 8.4 because 1.6 has two
significant figures.
16.2.5.6 Significant Figures in Addition and Subtraction

The result should have the same number of decimal places as the least precise measurement used in
the calculation. For example, in 15.62 + 12.5 + 20.4 = 48.52, the correct result is 48.5 because 12.5
has only one decimal place.
16.2.6 ROUNDING DATA

The following rules should be used in rounding data:
• If the digit to be removed is less than 5, the preceding digit stays the same. For example,
2.33 is rounded to 2.3.
• If the digit to be removed is greater than 5, the preceding digit is increased by 1. For ex-
ample, 2.36 is rounded to 2.4.
• If the digit to be removed is 5, round off the preceding digit to the nearest even number.
For example, 2.15 becomes 2.2 and 2.35 becomes 2.4.
L1572_C16 5/23/02 1:58 PM Page 256
16.2.7 EXPONENTIAL NOTATION

Exponential notation (e.g., 1.15 × 103 or 11.5 × 102) is an acceptable way to express both the number
and the significant figures. This form is not used in analytical reports, because it would be inconsis-
tent with the normal expression of the results and might be confusing. The general rule is that the re-
port should contain only figures that are justified by accuracy requirements of the analytical method.
16.3 RECORDS FOR RAW AND CALCULATED DATA

All documentation related to the raw data and the reported results should be in a bound form, easy to
identify, and ready for inspection at all times.
16.3.1 FIELD AND LABORATORY NOTEBOOK

A bound notebook is preferred to a loose-leaf one. The size of the notebook should be comfortable
to work with. Choose one that fits easily on the balance and working table, leaving space for glass-
ware, reagents, and other materials necessary for the analysis. Large notebooks, especially when
open, tend to get in the way and can cause spills and other problems. The first two pages should be
reserved for an index, in which page numbers and titles are listed. If the pages of the notebook are
not numbered, number each page in the upper right corner. Use the title heading to identify data on
each page and date it. Write all data in ink to avoid smearing and erasures. All raw data and obser-
vations should be written in the notebook. Nothing should be erased; cross out errors and unneces-
sary information with a single line, followed by an explanatory notation, initials, and date.
16.3.2 WORK SHEETS

Work sheets are drawn up for every analysis. The analyst must complete all parts of the work sheet
that contain the information relating to the sample (ID number, sample type, matrix, source, etc.), an-
alytical method or method number with reference, MDL (method detection limit), instrumentation,
analytical and QC raw data, calculated values, and proper measurement unit. The work sheet should
contain complete and clear information on all elements necessary for validation of the analytical
process. Tables 16.2, 16.3, and 16.4 provide general examples of forms used in recording various an-
alytical performances on diverse matrices for metals analysis. Documentation forms vary from one
institution or laboratory to another, according to requirements and preferences described and ap-
proved in respective QA/QC programs.
16.3.3 OTHER DOCUMENTATION

Documentation should be stored in bound form, with the date started, date ended, ID number started
and ended, document title, analytical group, and parameter prominent on covers. The storage area
should be large enough to keep records on shelves or in storage cabinets and easy to find. Strip charts,
AA calibration curves, and raw data collected should be stored in file boxes and identified as sug-
gested above.
16.3.4 DOCUMENTS TO BE SAVED

• Charts and other instrument-response readout records
• Calibration curves
• QC charts
• Target limits
• Method detection limits (MDLs)
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TABLE 16.2
Working Paper for Spectrophotometric Analysis (Water Samples)
Parameter___________Method No. _______________Reference __________________________________________

Method detection limit (MDL) ______________________________________________________________________
Model of spectrophotometer ___________________Wavelength __________________________________________
Correlation coefficient of calibration curve ___________________________________________________________
Analyzed by _______________________________________Date __________________________________________
ID Sample Sample Result

No. Identification Sample type (ml) Absorbance Dilution (mg/l) Remarks
Blank
Standard 1
CCS
CVS
Duplicate
Spike
Blank
INFORMATION RELATED TO QC CHECKS

% Recovery of Continuing Calibration Standard (CCS)_____________
True Value of Calibration Verification Standard (CVS) ______________
% Recovery of CVS ______________________ID of Duplicate Sample ______________________________________
ID No. of Spiked Sample _______________________Sample ml Spiked ______________________________________
Concentration of Spike Stock Solution___________Added Spike Value ______________________________________
Precision as Relative Percent Deviation (RPD) ____________________
Accuracy as % Recovery (%R) _________________________________
% Recovery of Spike (%Rsp)____________________________________
Approval of Supervisor ____________________________________Date ______________________________________

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TABLE 16.3
Working Paper for Spectrophotometric Analysis (Solid Samples)
Parameter___________Method No. _______________Reference __________________________________________

Method detection limit (MDL) ______________________________________________________________________
Model of spectrophotometer ___________________Wavelength __________________________________________
Correlation coefficient of calibration curve ___________________________________________________________
Analyzed by _______________________________________Date __________________________________________
ID Sample Final Tested Res Mois Rep. wet Rep. dry

No. Identification g (ml) (ml) Abs Dil (mg/l) (%) (mg/kg) (mg/kg)
Blank
Standard 1
CCS
CVS
Duplicate
Spike
Blank
INFORMATION RELATED TO QC CHECKS

% Recovery of Continuing Calibration Standard (CCS)_____________
True Value of Calibration Verification Standard (CVS) ______________
% Recovery of CVS ______________________ID of Duplicate Sample ______________________________________
ID No. of Spiked Sample _______________________Sample ml Spiked ______________________________________
Concentration of Spike Stock Solution ___________________________
ml or µl Spike Stock Added ____________________Added Spike Value ______________________________________
Precision as Relative Percent Deviation (RPD) ____________________
% Recovery of spike (%Rsp) ____________________________________
Approval of Supervisor ____________________________________Date ______________________________________

L1572_C16
TABLE 16.4
Working Paper for Atomic Absorption Spectroscopy
Parameter: ______________________________________________________ Model: _____________________________________________
5/23/02
Method No.: ____________________________________________________ Sensitivity Check: ____________________________________

Method Ref.: ____________________________________________________ Detection Limit: _____________________________________
Correlation Coefficient: __________________________________________ Analyzed by: ________________________________________
Wavelength: ____________________________________________________ Date: ______________________________________________
1:58 PM
Result Result
Sample Read abs. Dil. or Result Moisture
No. Matrix Sample (mg/kg (mg/kg Remarks
Identification (mg/l) Conc. (mg/l) (%)
wet base) dry base)
Page 259
g final ml
Blank
Standard low
mid
Converting Raw Data into Reportable Form
high
cont.
QC (CVS)
Sensitivity
check
Prep. blank
Lab. control
std. (LCS)
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Sample 6
Sample 7
Sample 8
Sample 9
Sample 10
Duplicate
spike
QC (CVS)
std. cont.
Blank
259
Note: Precision, RPD (relative percent deviation) = (A – B)/(A + B) × 200. Accuracy, as % Recovery on QC = (measured value × 100)/(true value). % Recovery on spike = [(spiked
sample value – sample value) × 100]/(true spike value). CVS = calibration verification standard.
L1572_C16 5/23/02 1:58 PM Page 260
• Summary log forms for precision and accuracy data

• Work sheets
• Records concerning receipt of stock solutions
• Preparation of calibration standards
• All notebooks, data forms, and log forms that pertain to laboratory operations
• Laboratory custody reports (holding times, sample transmittal forms, sample storage log,
sample disposal log)
• Sample preparation log
• All calculations related to sample results and statistical calculations for QC limits
• Instrument maintenance and instrument performance check logs
• Copies of final reports
• Field records such as field notebooks, field test data, and field custody record
Records should be retained for a period of at least 3 years. Drinking water reports require a retention
time of up to 10 years.
16.4 EVALUATION AND APPROVAL OF ANALYTICAL DATA

16.4.1 CHECKING CORRECTNESS OF ANALYSIS
To evaluate and approve reportable results, checks should be performed on sampling, sample han-
dling and storage, methodology calibration, and quality control. If problems arise because of suspect
data, initiation of corrective actions and providing the final approved results are the responsibility of
the analyst, the laboratory supervisor, and the QC department. Analytical data for each parameter
produced by the analyst are checked according to QC acceptance criteria, validated, corrected if nec-
essary, and then converted to a reportable value. The approved and checked analytical results for each
analyzed parameter are transferred to the sample report form. The sample report contains the results
for each requested parameter analyzed for a particular sample.
16.4.2 VALIDATION OF QC CHECKS

As discussed previously, QC checks are performed on analytical measurement results. When an error
occurs, it should be identified in detail, corrected, and replaced by a valid, reportable value. The re-
viewer should be focused on the acceptance criteria of the QC check, the probable source of the out-
of-control item, and the steps taken in the specified corrective action. The QC check must include QC
measures, such as blanks, calibration processes, QC check standards, QC check samples, certified
reference standards, matrix and reagent water spikes, duplicates, split samples, standardization of
titrant, instrument performance, proper storage of the reagents and standards, and quality checks of
laboratory-pure water. No data should be released until statistically supported limits are reported.
Data should be technically sound and defensible before reporting. The first requirement for report-
ing is that all pertinent documentation is available and referenced so that it can be consulted when-
ever a need arises.
16.4.2.1 Blanks
Analytical blanks measure the degree of contamination in a test and seriously affect the accuracy of
low-level determinations. Blank types include method, reagent, calibration, instrument, preparation,
blank, and trip, as described in Sections 13.5.3, 13.6.7, and 13.8.1. Note: Blank values should be less
than the method detection limit (MDL).
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16.4.2.1.1 Possible Causes of Unacceptable Blank Values

• Contaminated reagents
• Contaminated analyte-free water
• Contaminated glassware or sample containers
• Contaminated apparatus
• Contamination during sample collection and sample handling
• Contamination resulting from dirty laboratory environment or analyst’s clothing
16.4.2.2 Calibration
Calibration in chemical measurements is the process by which the response of a measurement sys-
tem is related to various concentrations of the analyte of interest. Generally, a measurement is a com-
parison process in which the unknown is compared with a known standard. (Calibration procedures
are discussed in Sections 6.6 and 13.6.) The first criterion for correct calibration is the purity and ac-
curacy of the standards. Standards may be prepared by the analyst or outside suppliers and should
have an assigned expiration date indicating stable life expectancy. Standards should never be used
beyond expiration dates.
16.4.2.2.1 Acceptance Criteria for Calibration
• The correlation coefficient should be at least 0.9950, but varies according to the analytical
method and instrumentation.
• Deviation of the continuing calibration standard (CCS) from the original calibration stan-
dard should be ±10% for inorganic analyses (±15% in organic analyses).
• Criteria for the calibration verification standard (CVS) or QC check sample (reference
standard) are generated in-house and cannot exceed the method range.
16.4.2.2.2 Probable Sources of Unacceptable Calibration
• Calculation error
• Incorrectly prepared stock and intermediate or calibration standards
• Outdated stocks and standards
• Faulty or expired QC check standard (CVS)
• Improperly stored stocks and standards
• Improperly selected and improperly used volumetric glassware
• Incorrect responses of the instrument
• Incorrectly cleaned glassware, containers, or dirty environment
Reanalyze all samples measured between the acceptable and unacceptable calibration check with the
corrected calibration.
16.4.2.3 Duplicates and Split Samples

Duplicates and split samples are used to measure the precision of the analytical system. Duplicate
types include field, laboratory, and matrix spike (Sections 13.5.3 and 13.8).
16.4.2.3.1 Accepted Limit or Target Limit
Calculated precision values vary by laboratory, parameter, and analytical method. When the meas-
ured and calculated precision values fall outside of this limit, corrective action is required to identify
the problem.
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16.4.2.3.2 Probable Sources and Correction of

Unacceptable Precision Values
• Sampling error for field duplicates: Review sample collection and preservation protocol.
Review sample preparation techniques and, if necessary, repeat the process for both du-
plicates and then reanalyze. If these activities do not resolve the problem, samples and du-
plicates should be redone.
• Preparation error for laboratory duplicates: A crowded work schedule in the laboratory
may cause the use of unidentical samples for duplication. Check carefully and identify the
sample for duplication prior to reanalyzing. Poor homogenization of the sample before du-
plication may also produce incompatible values.
• Contamination error: Different results for duplicate analyses are possibly caused by con-
tamination originating from improperly washed or stored glassware and equipment. Check
washing procedures and take all precautions to avoid contamination during duplication,
sample pretreatment, and analysis.
• Calculation error: Recheck all calculations related to the data in the report.
When these steps do not bring the analysis back within the acceptable precision limits, then the
entire analytical procedure must start again. It may be necessary to prepare new standards and cali-
brations. Other sample data generated with the same analytical run are questionable and must be re-
analyzed after the control limits are justified.
16.4.2.4 Spikes
All daily spiking data should agree with the spike accuracy limit established for each parameter and
analytical method.
16.4.2.4.1 Probable Sources of Unacceptable Spike Values
• Error during spike preparation
• Improperly prepared and stored spike stock solution
• Expired spike stock solution
• Contamination during spiking
• Instrument malfunction
All samples associated with the unacceptable spiked sample must be reprocessed and analyzed again
after correction.
16.4.2.5 Analytical Performance Checks

To validate the analytical system or measurement process, laboratories use performance evaluation
samples. Internal reference standards are prepared by the laboratory. External reference materials
are provided by an outside source and may originate from a technically acceptable and certified or-
ganization. Analytical values should be within the certified limits.
16.4.2.5.1 Causes of Performance Check Failure
• Improper sample preparation
• Improper analysis; if samples were concentrated or diluted to the proper range of the
analysis, carefully check these techniques and the accompanying calculations
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• Contamination error; after correction, reprocess and reanalyze all samples that were meas-
ured at the same time as the failed reference standard
16.4.2.6 Quality of Laboratory Pure Water

Acceptance criteria for the quality of laboratory pure water are discussed in Section 13.4. If the meas-
ured values deviate from this standard, corrective action is needed immediately. Change the car-
tridges and call the contracted company for regular maintenance of the system.
16.4.3 DOCUMENTATION OF OUT-OF-CONTROL CONDITIONS

All out-of-control conditions must be documented immediately by personnel at all levels of respon-
sibility. Documentation by the analyst is done by plotting the out-of-control data on the QC charts
and labeling the sample results pertaining to that test parameter as “suspect data.”
The laboratory supervisor will document all “out-of-control” conditions by issuing a noncom-
pliance report to the quality assurance (QA) officer. The report must include the out-of-control test
parameter, date of occurrence, ID number, copy of the failed QC data, description of the analytical
problem, and the corrective action. The QA officer will issue a written report to the laboratory man-
ager defining any QC noncompliance occurrence and specifying suspect sample data. The report
must include the out-of-control parameter, date, time, ID numbers of samples containing suspect
data, description of the QC problem, and the corrective action. A typical noncompliance report form
is shown in Table 16.5.
TABLE 16.5
Noncompliance Report Form
QC
Test Out of Date of Name of Suspect QC
Measured (%R) (%R) Limit
Control Problem Analyst Samples ID True Value
Value
Description of Analytical Problem
Corrective Action
Laboratory supervisor ____________________________________ Date ____________________________

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Reporting Analytical Data

17
Reports are the written records of analytical work. The content of analytical reports should include
all necessary information presented in a transparent and well-organized fashion. The designer of the
final report must keep in mind that the reader frequently does not understand the results generated by
instruments and laboratory protocols. Brief interpretation of the reported values is essential.
Chapter 16 discusses how analytical data are calculated and checked. Never issue a report until
all checks have been completed and approved.
17.1 REQUIRED DOCUMENTATION

All documentation used to approve and defend reported data must be collected and should be avail-
able and referenced so that it can be consulted whenever necessary. The content of these documents
should be detailed and clear enough to explain to the interested party how the final reported values
were generated.
17.1.1 DOCUMENTATION REQUIRED TO APPROVE AND DEFEND

REPORTED DATA
17.1.1.2 Documentation for Sample Collection and Identification
• Sampling plan and sample collection methods
• Field QC
• Sample identification and chain of custody
• Field notebook and documentation of field tests
17.1.1.3 Documentation of Analytical Performance

• Analytical method used and method detection limit (MDL)
• Instrumentation (manufacturer, model, performance checks, maintenance log)
• Calibration data (initial and continuing)
• Detailed analytical work (work sheets, standards and reagent preparation, calculations)
17.1.1.4 QA/QC Documentation and Data

• Analysis of blanks
• Precision and accuracy data
• QC charts
• Acceptable ranges for precision and accuracy per parameter
• Source of QC check standards
• Preparation of spike stock solution and how spikes were prepared
265
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17.1.1.5 Checks and Validation of Analytical Data

• Documentation of how analytical data were checked and validated
• Corrective actions (when applicable)
• Date and signature of approval of reportable data for each parameter tested
• Date and signature of approval for final analytical report
17.2 SIGNIFICANT FIGURES IN ANALYTICAL REPORTS

Numerical data are often obtained with more digits than are justified for required accuracy and pre-
cision. Report only figures that are justified by the accuracy of the analytical method. Do not use the
common practice of making all numbers in one column have the same number of significant figures
to the right of the decimal point. The reported numbers pertain to different parameters and they are
analyzed by different methods, so the significant figures will also be different. Significant figures are
discussed in Section 15.5.
• If an analytical result is 16.6 mg/l, and the analyst is certain of the 16 but not certain of the
0.6, the rounded-off result reported should be 17.
• When an analytical result is 16.61 and is generated by a method that justifies these signif-
icant figures, the reported number should be 16.61.
• If a calculated value is 2346 mg/l, but the analyst is not certain about the last two numbers,
the rounded-off number reported should be 2350.
• If a number is written as 5.000, it is understood that the zeros are significant, or the num-
ber would have to be rounded off to 5.00, 5.0, or 5, whichever is appropriate.
• If a result is 360 mg/l, there should be certainty that the zero is significant and cannot be
deleted.
17.3 UNITS USED TO EXPRESS ANALYTICAL RESULTS

Measurement units used to express analytical results depend on the analytical method used, the con-
centration of the analyte, and the matrices of the sample analyzed. The most common unit used to
express analytical results in environmental samples is ppm. This unit is equal to milligram per liter
(mg/l) or milligram per kilogram (mg/kg).
When the concentration is less than 0.1 ppm, it is more convenient to express the result as ppb,
microgram per liter (µg/l), or microgram per kilogram (µg/kg).
If the concentration is greater than 10,000 ppm, the result is expressed as a percent (%). One per-
cent (1%) is equal to 10,000 ppm when the specific gravity is 1.0.
If the result is issued in ppm or percent by weight for solid samples or liquids with high specific
gravity, a correction is necessary as follows:
mg/kg = (mg/l)/specific gravity (17.1)
% by weight = (mg/l)/(10,000 × specific gravity) (17.2)
Analytical results for solid samples are reported in milligrams per kilogram (mg/kg) or micro-
grams per kilogram (µg/kg), or, as stated above, as percentages (%), according to the concentration
value. The report must also indicate that the result is on an “as-is basis” (also called “wet base”) of
the solid, when the solid is not corrected to a dry, moisture-free solid. When results are reported on
the “dry base,” the value is corrected to dry, moisture-free solid. Calculation of these units is dis-
cussed in Section 16.2.2 and Appendix I.
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Reporting Analytical Data 267
Calculations related to water treatment require analytical results in milliequivalents per liter
(meq/l). Conversion of milligrams per liter to millequivalents per liter are discussed in Section 16.2.3.
17.4 CONFIDENCE INTERVAL

Reporting the calculated confidence interval (CI) of a measurement helps the reader to estimate the
reliability of the result. The calculated confidence interval is rounded to two significant figures in re-
ports. Usually the 95% confidence limit is used in the calculation. Calculation of CIs is discussed in
Section 13.10.2.3.
17.5 REPORT FORMAT

A simple tabular form is acceptable for regular, routine reporting. It should be clear, easy to follow,
and contain all necessary information to evaluate the analytical report. For special, nonroutine pur-
poses, reports are more detailed, and a comprehensive QA/QC report should be attached to the ana-
lytical report.
Title: The title should be brief but descriptive and identify the goal of the analytical work.
Who requested the analysis: Identify the organization or person for whom the work was done,
including name, organization, address, phone number, work order, and so on.
Report number: Provide the laboratory identification number (ID number, such as calendar
year/sequence number).
Date: Provide date the report was completed.
Objective: Include a short statement about the reason the work was done.
Sample identification: Provide a physical description of the sample, sampling area, and all in-
formation related to the sample that may impact the data. If possible, include a photograph
of the sampling area.
Sampling details: This information includes sampling procedures, sample type, sample preser-
vation, name of the sample collector, date and time of the collection, chain of custody, sam-
ple field custody and transportation.
Analyzed parameters with method numbers and method references: References should be spe-
cific and provide all necessary information (reference number, revision date, etc.).
Modifications of the original method should be stated.
Method detection limit (MDL) or practical quantitation limit (PQL): Provide the specified
MDL or PQL for each analysis.
Numerical values and units: Numerical values are reported with correct significant figures and
corresponding unit.
References: Provide information related to previous analytical work, references to other reports
on the same sample location.
Precision and accuracy data: State the precision and accuracy data with the acceptance limit
for each analytical performance.
Discussion: This secton includes interpretation of the results, recommendation of additional
work or corrections, and any special observations related to the sample or the analytical re-
port that serves the objective of the analysis.
Signatures: Include signatures and titles of all persons responsible for the data and the report.
Distribution list: Provide the full distribution list of the report.
Attachment: Attach the QC report, which contains the basis of calibration, standardization,
statement, and where the documentation is found. Precision and accuracy data with corre-
sponding acceptance limits should be included for each analytical performance.
The pages of the report should be properly numbered. Readers must be certain that they have the full
report for review (e.g., use page 1 of 5, page 2 of 5, etc.).
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Selected Methods for

18 Determination of Metals in
Environmental Samples
18.1 METHODOLOGY
Methods are developed to analyze diverse media for specific parameters. Each method is approved
by the Environmental Protection Agency (EPA), which specifies the procedures, instrument calibra-
tion, sample preparation, analytical procedures, and quality control requirements for the analytical
work. EPA methods are differentiated according to the media (matrix) of the sample analyzed. Each
laboratory has a written guidebook that contains specific procedures used, known as standard oper-
ating procedures (SOPs). SOPs should be constantly revised to include new methodologies and pro-
cedural changes. The SOPs are an important tool for the quality assurance/quality control (QA/QC)
operation of the laboratory.
18.1.1 EPA-APPROVED METHODS AND REFERENCES

FOR ANALYZING WATER SAMPLES
18.1.1.1 Methods and References for Analyzing Drinking Water

Methods for Chemical Analysis of Water and Wastes (EPA 600/4–79–020, revised March 1983)
Methods for Determining Organic Compounds in Drinking Water (EPA 600/4–88–039,
December 1988)
Standard Methods for the Examination of Water and Wastewater (APHA-AWWA-WPCF, 19th
ed., 1998) (an updated edition is issued every 5 years)
Manual for Certification of Laboratories Analyzing Drinking Water (EPA 570/9–90/008, April
1990)
CFR Part 141, Subpart C and Subpart E (monitoring and analytical requirements)
EPA 500 series (should be used for organic analyses of drinking waters and raw source waters)
18.1.1.2 Methods and References for Analyzing Surface Waters

and Wastewater Effluents
Methods for Chemical Analysis of Water and Wastes (EPA 600–4–79–020, revised in
March 1983)
Test Methods for Evaluating Solid Waste (EPA SW-846, 3rd ed., 1986; rev. ed., December
1987)
40 CFR, Part 136 (Tables IA, IB, IC, ID, and IE, July 1989)
269
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18.1.1.3 Methods and References for Analyzing Water Sources (Surface and
Groundwater) Pursuant to 40 CFR Part 261 (RCRA)
1987) 40 CFR, Part 261 (Methods, Appendix III, 1989)
USEPA Contract Laboratory Program Statement of Work for Inorganic Analyses (EPA SOW
ILMO3.0, March 1990)
USEPA Contract Laboratory Program Statement of Work for Organic Analyses (EPA SOW
OLMO3.1, August 1994)
18.1.1.4 Methods and References for Microbiological and Biological Tests

of Water Samples
Microbiological Methods for Monitoring the Environment (EPA 600/8–78–017, 1987)
40 CFR, Part 141 (Subpart C, monitoring and analytical requirements, July 1989)
40 CFR, Part 136 (Table IA, July 1989)
Methods for Measuring the Acute Toxicity of Effluent to Freshwater and Marine Organisms
(EPA 600/4–85–013, 3rd ed., 1985)
Short-Term Methods for Estimating the Chronic Toxicity of Effluent and Receiving Waters to
Freshwater Organisms (EPA 600/4–89–1990)
Short-Term Methods for Estimating the Chronic Toxicity of Effluent and Receiving Waters to
Marine and Estuarine Organisms (EPA 600/4–87–028, 1988)
18.1.2 EPA-APPROVED METHODS AND REFERENCES FOR ANALYZING

SEDIMENTS AND RESIDUALS
18.1.2.1 Methods and References for Analyzing Soils, Sediments,
Domestic and Industrial Sludges, Solid and Hazardous Wastes
1987)
40 CFR, Part 261 (Appendix III, July 1989)
Procedures for Handling and Chemical Analysis of Sediments and Water Samples (EPA/Corps
of Engineers, CE-81–1, 1981)
USEPA Contract Laboratory Program Statement of Work for Inorganic Analysis (EPA SOW
ILMO3.0, March 1990)
USEPA Contract Laboratory Program Statement of Work for Organic Analysis (EPA SOW
OLMO3.1, August1994)
POTW Sludge Sampling and Analysis Guidance Document (EPA Permits Division,
August 1989)
18.1.3 APPROVED MODIFICATION OF EPA METHODS

18.1.3.1 EPA Method 300.0
This method may be used for the analysis of specified ions in ground water and surface water, except
for fluoride. It is currently approved for drinking water analysis.
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Selected Methods for Determination of Metals in Environmental Samples 271
18.1.3.2 EPA Methods 601, 602, 624, and 625

Capillary columns may be used instead of the specified packed columns if the laboratory meets the
pertinent accuracy and precision criteria and detection limit with this modification.
18.1.3.3 EPA Methods 601 and 602

The photoionization detector and electrolytic conductivity detector may be used in a series if the lab-
oratory can meet the performance criteria.
18.1.3.4 EPA Methods 602, 8020, 8021

These methods may include analysis of xylene and methyl-tert-butyl-ether (MTBT).
18.1.3.5 EPA Methods 610, 625, 8100, 8310, 8250, 8270

These methods may include analysis of methylnaphthalenes.
18.1.3.6 EPA Method 5030/8010

This method must be modified to analyze EDB in soils. An electron-capture detector instead of an
electrolytic conductivity detector must be used.
18.1.4 EPA CONTRACT LABORATORY PROTOCOL (CLP)

This protocol was developed for the Superfund program. CLP specifies a set of methods based on the
existing methodology for organic and inorganic parameters, but which are modified to incorporate
certain quality control, calibration, and deliverable requirements. The data package includes a full
reporting of quality control procedures and data, making it particularly useful if litigation is a possi-
bility. The results of the analyses are provided in many different formats, ranging from a sample re-
port only to a full-documentation data package.
The CLP, as stated in the EPA statement of work (SOW), has a high level of quality assurance re-
quirements. The deliverable requirements include quality control summaries (method blank, initial
calibration verification, duplicate analysis, and matrix spike/matrix spike duplicates) and quality
control data, as well as data on a diskette. Consequently, CLP has become a commonly requested
methodology and has the effect of separating larger laboratories — which have the equipment, cer-
tifications, and trained personnel capable of producing data according to this protocol — from the
thousands of smaller environmental laboratories which do not.
Because EPA methods, as now written, are not interchangeable, it is very difficult for an analyt-
ical laboratory to accommodate all quality control criteria for all methods. Thus, the EPA’s current
intent is to create a unified method to minimize the requirement differences.
18.1.5 DETERMINATION OF SELECTED METALS IN ENVIRONMENTAL SAMPLES

Table 18.1 summarizes the methods, method numbers, and references used for determination of met-
als in environmental samples.
18.2 ALUMINUM
Aluminum (Al) is the third most abundant element of the Earth’s crust, occurring in mineral rocks
and clays. Soluble, insoluble, and colloidal aluminum may appear in treated water or wastewater as
L1572_C18 5/23/02 1:59 PM Page 272
TABLE 18.1
Methods for Determination of Metals
Parameter FL GR Other Method No. Ref. Method No. Ref.

Aluminum + + — 202.1&2 R-1 7020 R-3
Antimony + + — 204.1&2 R-1 7040 R-3
Arsenic – + — 206.2 R-1 7060 R-3
Barium + + — 208.1&2 R-1 7080 R-3
Beryllium + + — 210.1&2 R-1 7090 R-3
Boron – – Curcumin 4500-BB R-2 — —
Boron – – Carmine 4500-BC R-2 — —
Cadmium + + — 213.1&2 R-1 7130 R-3
Calcium + – — 215.1 R-1 7140 R-3
Calcium – – EDTA titrimetric 215.2 R-1 — —
Chromium + + — 218.1&2 R-1 7190 R-3
Chromium6+ – – Colorimetric 3500CrD R-2 7196 R-3
Cobalt + + — 219.1&2 R-1 7200 R-3
Copper + + — 220.1&2 R-1 7210 R-3
Iron + + — 236.1&2 R-1 7380 R-3
Lead + + — 239.1&2 R-1 7420 R-3
Magnesium + + — 242.1&2 R-1 7450 R-3
Manganese + + — 243.1&2 R-1 7460 R-3
Mercury – – Cold vapor 245.1. R-1 7470, 7471 R-3
Molybdenum + + — 246.1&2 R-1 7480 R-3
Nickel + + — 249.1&2 R-1 7520 R-3
Potassium + – — 258.1 R-1 7610 R-3
Selenium – + — 270.2 R-1 7740 R-3
Silver + + — 272.1&2 R-1 7760 R-3
Sodium + – — 273.1 R-1 7770 R-3
Thallium + + — 279.1&2 R-1 7840 R-3
Tin + + — 282.1&2 R-1 7870 R-3
Titanium + + — 283.1&2 R-1 — —
Vanadium + + — 286.1&2 R-1 7910 R-3
Zinc + + — 289.1&2 R-1 7950 R-3
Note: Metals analysis by inductively coupled plasma (ICP) method is widely used according to method 6010, with reference
to R-3. Fl = flame atomic absorption technique; Gr = graphite furnace atomic absorption technique; R-1 = methods for
Chemical Analysis of Water and Wastes (EPA-600/4-79-020, Revised March 1983); R-2 = Standard Methods for the
Examination of Water and Wastewater (AWWA, 18th ed., 1992); R-3 = Test Methods for Evaluating Solid Wastes (EPA SW-
846 EPA SW-846, 3rd ed., 1986).
a residual of coagulation with aluminum-containing material. Filtered water from a modern, rapid-
sand filtration plant should have an aluminum concentration less than 50 µg/l.
Selection of method: The FAAS, GrAAS, and ICP methods are preferred. For discussion of in-
strumentation and analysis procedures, see Chapters 8, 9, and 12, respectively.
18.2.1 FLAME ATOMIC ABSORPTION SPECTROSCOPY (FAAS)

Aluminum may be as much as 15% ionized in a nitrous oxide/acetylene flame. Use an ionization sup-
pressor of 1000 µg/ml K as KCl (dissolve 95 g of KCl and dilute to 1000 ml). The calibration stan-
dards should contain the same type of acid in the same concentration as in the sample (usually 5
ml of acid per 100 ml), and 2 ml/100 ml of KCl solution as suppressor (see above).
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18.2.1.1 Instrument Parameters

• Instrument: Aluminum hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Nitrous oxide
• Type of flame: Rich fuel
• Background correction: Not required
18.2.1.2 Performance Characteristics

• Optimum concentration range: 5 to 50 mg/l
• Detection limit: 0.1 mg/l
• Sensitivity: 1 mg/l
• Wavelength: 309.3 nm
18.2.2 GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY (GRAAS)

Background correction may be required if the sample contains highly dissolved solids. Chloride ion
and nitrogen used as a purge gas reportedly suppress the aluminum signal; therefore, the use of halide
acids and nitrogen as a purge gas should be avoided.

• Drying time and temperature: 30 sec at 125°C
• Ashing time and temperature: 30 sec at 1300°C
• Atomizing time and temperature: 10 sec at 2700°C
• Purge gas: Argon
Other operating parameters should be set as specified by the instrument manufacturer.

• Detection limit: 3 mg//l
18.3 ANTIMONY
The level of antimony (Sb) present in natural waters is usually less than 10 µg/l and may be present
in higher concentrations in hot springs or waters draining mineralized areas. Antimony is a regulated
contaminant under various federal and state programs.
Selection of method: The GrAAS method (Chapter 8) is the method of choice because of its sen-
sitivity. Alternatively, use the FAAS method (Chapter 9) or the ICP method (Chapter 12) when high
sensitivity is not required.

In the presence of lead (1000 mg/l), spectral interference may occur at the 217.6-nm resonance line.
In this case, the 231.1-nm antimony line should be used.
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• Instrument: Antimony hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air
• Type of flame: Lean fuel

• Sensitivity: 0.5 mg/l

High Pb concentration may cause a measurable spectral interference on the 217.6 nm-line. In this
case, a secondary wavelength or Zeeman background correction should be used. See Chapter 9 for
general discussion of the furnace technique. A soft-digestion procedure is the only recommended one
for Sb, as discussed in Sections 15.2.2 and 15.8. The addition of HCl to the digestate prevents fur-
nace analysis of many metals.

• Purge gas: Argon or nitrogen
• Wavelength: 217.6 nm (primary); 231.1 nm (alternate)
• Background correction: Required

• Detection limit: 3 mg/l
The above concentration values and instrument conditions are based on the use of a 20-µl injection,
continuous-flow purge gas and nonpyrolytic graphite. See instrument manufacturer’s operations
manual for information.
18.4 ARSENIC
Severe poisoning can arise from the ingestion of arsenic trioxide (As3O2) in amounts as small as 100 mg;
chronic effects may result of the accumulation of arsenic compounds in the body at low intake levels.
Carcinogenic properties are also known. The toxicity of arsenic depends on its chemical form. The
As concentration in potable waters is usually less than 10 µg/l, but values as high as 100 µg/l have
been reported. Aqueous arsenic may result from mineral dissolution, industrial discharges, or the ap-
plication of herbicides.
Selection of methods: The hydride-generation atomic absorption method (Chapter 11) is the
method of choice, although the GrAAS (Chapter 9) is simpler.
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18.4.1 GASEOUS HYDRIDE ATOMIC ABSORPTION METHOD

This method is applicable for sample matrices that do not contain high concentrations of Cr, Cu, Hg,
Ni, Ag, Co, and Mo. Instrumentation and analytical procedures are discussed in Chapter 11. The typ-
ical detection limit for this method is 0.002 mg/l.

Following the appropriate dissolution (acid digestion) of the sample, a representative aliquot of the
digestate is spiked with nickel nitrate solution and is placed manually or by means of an automatic
sampler into a graphite furnace. See Chapter 9 for details of the GrAAS technique.


18.4.2.3 Interferences
Elemental As and many of its compounds are volatile; therefore, samples may be subject to losses of
As during sample preparation. Spike samples and standard reference materials should be processed
to determine if the chosen dissolution method is appropriate.
Caution must be employed during the selection of temperature and times for the dry and char cy-
cles. A nickel nitrate solution must be added to all digestates prior to analysis to minimize volatiliza-
tion losses during drying and ashing.
Arsenic analysis may be subject to severe nonspecific absorption and light scattering caused by
matrix components during atomization. Aluminum is a severe positive interferant in the analysis of
arsenic. Zeeman background correction is very useful in this situation.
If the analyte is not completely volatilized and removed from the furnace during atomization,
memory effects will occur. If this situation is detected by means of blank burns, the tube should be
cleaned by operating the furnace at full power at regular intervals during the analysis.
18.4.2.4 Reagents
• Concentrated HNO3
• Hydrogen peroxide, H2O2 (30%)
• As stock solution, 1000 mg/l (commercially available or prepared according to recipe in
Appendix H)
• Nickel nitrate, 5% (dissolve 24.780 g of Ni(NO3)2.6H2O in reagent-grade water and dilute
to 100 ml)
• Nickel nitrate, 1% (dilute 20 ml of the 5% nickel nitrate solution to 100 ml with reagent-
grade water)
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18.4.2.5 Procedure
1. Prepare samples for the analysis as described in Sections 15.6.2 and 15.6.3.
2. Pipet 5 ml of digested solution into a 10-ml volumetric flask, add 1 ml of the 1% nickel
nitrate solution, and dilute to 10 ml with reagent-grade water. The sample is ready for in-
jection into the furnace.
3. The 193.7-nm wavelength line is recommended.
4. A background correction system is required. For other spectrophotometric parameters,
follow the manufacturer’s instructions.
5. Furnace parameters suggested by the manufacturer should be employed as guidelines.
Because temperature-sensing mechanisms and temperature controllers can vary among in-
struments or with time, the validity of the furnace parameters must be periodically con-
firmed by systematically altering the furnace parameters while analyzing a standard. In
this manner, losses of analyte due to overly high temperature settings or losses in sensi-
tivity due to less-than-optimum settings can be maintained. Similar verification of furnace
parameters may be required for complex sample matrices.
6. Calibration curves must be composed of a minimum of a blank and three standards. A cal-
ibration curve should be made for every hour of continuous sample analysis.
7. Inject a measured microliter aliquot of sample into the furnace and atomize. If the con-
centration found is greater than the highest standard, the sample should be diluted in the
same acid matrix and reanalyzed. The use of multiple injections can improve accuracy and
help detect furnace pipeting errors.
8. Run a check standard after every ten injections of samples. Standards are run in part to
monitor the life and performance of the graphite tube. Lack of reproducibility or sig-
nificant change in the signal for the standard indicates that the graphite tube should
be replaced.
9. Employ a minimum of one blank with a sample batch to verify any contamination.
10. The standard addition method (Section 7.7.1.1.1) should be employed for the analysis of
all EPTOX extracts.
11. QC requirements are listed in Chapter 13.
18.5 BARIUM
Barium (Ba) stimulates the heart muscle. However, a barium dose of 550 to 600 mg is considered
fatal to human beings. Despite its relative abundance in nature (16th in order of rank), barium occurs
only in trace amounts in water (0.7 to 900 µg/l, with a mean of 49 µg/l). Higher concentrations in
drinking water often signal undesirable industrial waste pollution.
Selection of method: Preferably, analyze via the FAAS (Chapter 8), GrAAS (Chapter 9), or ICP
(Chapter 12) method.

The FAAS technique is described in Chapter 8. A high, hollow, cathode-current setting and a narrow
spectral band pass must be used, because both barium and calcium emit strongly at barium’s analyt-
ical wavelength. Barium undergoes significant ionization in the nitrous oxide/acetylene flame, re-
sulting in a significant decrease in sensitivity. All samples and standards must contain 2 ml of potas-
sium chloride (KCl) ionization suppressant per 100 ml of sample. (Dissolve 95 g of KCl in reagent-
grade water and dilute to 1 liter.)
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Prepare calibration standards via dilutions of the stock solution at the time of analysis. The cali-
bration standards should be prepared to contain the same type and concentration of acid as the sam-
ples to be analyzed after digesting. All calibration standards should contain 2 ml of the KCl (ioniza-
tion suppressant) solution.

• Instrument: Barium hollow cathode lamp
• Fuel: Acetylene


The use of halide acid should be avoided. Because of possible chemical interaction, nitrogen should
not be used as a purge gas.


18.6 BERYLLIUM
Beryllium (Be) and its compounds are very poisonous and in high concentrations can cause death.
Inhalation of beryllium dust can cause a serious disease called berylliosis. Beryllium disease also can
cause dermatitis, conjunctivitis, acute pneumonitis, and chronic pulmonary berylliosis. Beryllium is
used in atomic reactors, aircraft, rockets, and missile fuels. Entry into water can result from the dis-
charges of these industries. The usual range of beryllium in drinking waters is 0.01 to 0.7 µg/l.
Selection of methods: FAAS, GrAAS, and ICP methods may be used (see Chapters 8, 9, and 12,
respectively).
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Background correction may be required. Concentration of aluminum greater than 500 ppm may sup-
press beryllium absorbance. The addition of 0.1% fluoride has been found effective in eliminating
this interference. High concentrations of magnesium and silicon cause similar problems and require
the use of the standard additions method.

• Instrument: Beryllium hollow cathode lamp
• Fuel: Acetylene

• Optimum concentration range: 0.05 to 2 mg/l
For concentrations below 0.02 mg/l, the furnace procedure is recommended.

Long residence time and high concentrations of the atomized sample in the optical path of the
graphite furnace can result in severe physical and chemical interference. Furnace parameters must be
optimized to minimize these effects. In addition to the normal interferences experienced during
graphite furnace analysis, beryllium analysis is subject to severe nonspecific absorption and light
scattering during atomization. Simultaneous background correction is required to avoid erroneous
high results.

The above concentration values and instrument conditions are for a Perkin Elmer HGA-2100,
based on the use of a 20-µl injection, continuous-flow purge gas, and nonpyrolytic graphite. Smaller
sizes of furnace devices or those employing faster rates of atomization can be operated using lower
atomization temperatures for shorter time periods than the recommended settings above.

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18.7 BISMUTH
Bismuth is extremely insoluble in natural waters and is generally present only in trace amounts (less
than 10 µg/l). It may be present in higher concentrations in waters draining mineralized areas.

See Chapter 8.
18.8 CADMIUM
Cadmium (Cd) is highly toxic and has been implicated in some cases of poisoning through food. A
cadmium concentration of 200 µg/l is toxic for certain fish. Cadmium may enter water as a result of
industrial discharges or the deterioration of galvanized pipes.
Selection of methods: The GrAAS method (Chapter 9) is preferred. The FAAS (Chapter 8) and
ICP (Chapter 12) methods provide acceptable precision and bias with higher concentration limits.

Nonspecific absorption and light scattering can be significant at the analyte wavelength. Background
correction is required.

• Instrument: Cadmium hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air
• Type of flame: Oxidizing (lean fuel)

For concentrations of cadmium below 0.02 mg/l, the furnace procedure is recommended.

In addition to the normal interferences experienced during graphite furnace analysis, cadmium analy-
sis may be subject to severe nonspecific absorption and light scattering caused by matrix components
during atomization. Simultaneous background correction is required to avoid erroneous high results.
Excess chloride may cause premature volatilization of cadmium. Ammonium phosphate used as
a matrix modifier minimizes this loss.
Calibration standards should be prepared at the time of analysis. To each of the 100-ml standards
and the sample, add 2.0 ml of 40% ammonium phosphate solution (40 g (NH4)2HPO4 per 100 ml of
reagent-grade water). The calibration standards should be prepared to contain 0.5% (v/v) HNO3.
Many plastic pipet tips (yellow) contain cadmium. Use “cadmium-free” tips.
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based on the use of a 20-µl injection, continuous-flow purge gas and nonpyrolytic graphite. Smaller
atomization temperatures for shorter time periods than the above-recommended settings.
18.9 CALCIUM
The presence of calcium (Ca, fifth among the elements in order of abundance) in water supplies re-
sults from the passage of water through or over deposits of limestone, dolomite, gypsum, and gyp-
siferous shale. Cadmium content may range from zero to several hundred milligrams per liter. Small
concentrations of calcium carbonate combat corrosion of metal pipes by laying down a protective
coating. Appreciable quantities of calcium salts, on the other hand, precipitate on heating to form
harmful scale in boilers, pipes, and cooking utensils. Calcium contributes to the total hardness of
water. Chemical softening treatment, reverse osmosis, electrodialysis, or ion exchange is used to re-
duce calcium and associated hardness.
Selection of method: FAAS (Chapter 8) and ICP (Chapter 12) methods are accurate means of de-
termining calcium. The EDTA (ethylene diamine tetraacetic acid) disodium salt titration method pro-
vides good results for control and routine applications.

All elements forming stable oxyanions will complex calcium and interfere unless lanthanum is
added. The addition of lanthanum to prepared samples rarely presents a problem because virtually all
environmental samples contain sufficient calcium to require dilution to obtain results in the method’s
linear range. Phosphates, sulfates, and aluminum, as well as high concentrations of magnesium,
sodium, and potassium are interferants.
Calibration standards should be prepared at the time of the analysis and should contain the same
type of acid and at the same concentrations as the preserved samples. Add 1 ml of lanthanum chlo-
ride solution (carefully dissolve 29 g of La2O3 in 250 ml of concentrated HCl and dilute to 500 ml
with reagent-grade water) per 10 ml of standards and samples.

• Instrument: Calcium hollow cathode lamp
• Fuel: Acetylene
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• Type of flame: Stoichiometric

18.9.2 Determination of Hardness by EDTA Titrimetric Method

The EDTA disodium salt forms a chelated soluble complex when added to a solution of certain metal
cations. If a small amount of dye such as Eriochrom black T is added to an aqueous solution contain-
ing calcium and magnesium ions at a pH of 10, the solution becomes wine red. If EDTA disodium salt
is added as a titrant, the calcium and magnesium will be complexed, and the solution turns from red
wine to blue, marking the endpoint of the titration. The sharpness of the endpoint increases with in-
creasing pH. Magnesium ions must be present for a satisfactory endpoint. To ensure the presence of Mg
ions, a small amount of complexometrically neutral magnesium salt of EDTA is added to the buffer.
18.9.2.1 Apparatus and Materials

• Buret, 25 ml or 50 ml
• Volumetric pipets, 5 ml, 10 ml, 25 ml
• Graduated cylinders, 100 ml
• Mohr pipets, 5 ml
• Erlenmeyer flasks, 250 ml
• Volumetric flasks, various sizes
• Disposable transfer pipets
• Magnetic stirrer
• Teflon magnetic stirring bars
• pH paper, full range
18.9.2.2 Reagents
18.9.2.2.1 Buffer Solution
1. Solution 1:
a. Weigh 1.179 g of EDTA disodium salt (Na2EDTA) and transfer to a 150-ml beaker.
b. Weigh 0.780 g of magnesium sulfate heptahydrate (MgSO4.7HO) or 0.644 g of magne-
sium chloride hexahydrate (MgCl2.6H2O) and transfer to the same beaker.
c. Add deionized (DI) water to the beaker until the volume is about 100 ml and mix until
solids are dissolved.
2. Solution 2:
a. Weigh 16.9 g of ammonium chloride (NH4Cl), transfer into a 250-ml volumetric flask, and
add 143 ml concentrated ammonia solution (NH4OH).
b. Transfer solution 1 from the beaker into solution 2 in the 250-ml volumetric flask. Rinse
the beaker well with DI water and add the rinsate to the volumetric flask. Fill to 250 ml
with DI water. Stopper the volumetric flask and mix well. Store buffer solution in poly-
ethylene bottle and tighten stopper.
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The buffer solution can be used for about 1 month. Discard the buffer when 1 or 2 ml are added to
the sample and it fails to produce a pH of 10.0 at the titration endpoint.
18.9.2.2.2 Eriochrom Black T Indicator
Weigh 0.5 g of indicator and 100 g of NaCl into a porcelain mortar, and mix well. Alternatively, a
coffee grinder may be used for complete mixing.
18.9.2.2.3 0.02N EDTA Titrant
Dissolve 3.723 g of EDTA disodium salt in about 700 ml of DI water in a 1-liter volumetric flask and
dilute to the mark with DI water. Standardize against standard 0.02N CaCO3 solution.
18.9.2.2.4 Calcium Carbonate Standard Solution
Weigh 1.0000 g of anhydrous CaCO3 (primary standard) and transfer to a 500-ml Erlenmeyer flask.
Place a funnel in the flask neck and add drops of 1+1 HCl solution until all CaCO3 is completely dis-
solved. Add 200 ml of distilled water and boil for a few minutes to expel CO2. Cool at room temper-
ature. Add a few drops of methyl red indicator while stirring. Adjust the color, while stirring, to an
intermediate orange color with 3N NH4OH or 1+1 HCl. Transfer quantitatively into a volumetric
flask and dilute to 1 liter with DI water. Store in a polyethylene bottle.
1 ml = 1 mg CaCO3
18.9.2.2.5 Reference Stock Solution, 33,333 mg/l Total Hardness, as CaCO3

Transfer 12.4860 g of anhydrous, primary-standard calcium carbonate (CaCO3) into a 1-liter volu-
metric flask. Add about 200 ml of DI water and slowly add concentrated hydrochloric acid (HCl)
until calcium carbonate is completely dissolved. Transfer 19.5847 g of anhydrous magnesium chlo-
ride (MgCl2) into the 1-liter volumetric flask containing the calcium carbonate solution. Mix well for
complete dissolution and fill up to the 1-liter volume. Mix well again. The solution contains 33,333
mg/l total hardness as CaCO3.
18.9.2.2.6 Reference (Independent) Standard, 166 mg/l Total Hardness as
CaCO3
Pipet volumetrically 5 ml of the reference stock solution into a 1-liter volumetric flask and dilute to
the required volume with DI water. This solution is the actual working reference with a value of 166
mg/l total hardness as CaCO3.
18.9.2.2.7 Standardization of EDTA Titrant with CaCO3 Standard Solution
1. Pipet 10 ml of CaCO3 standard solution into a 100-ml Erlenmeyer flask.

2. Using a Mohr pipet, add 5 ml of buffer solution and one scoopful of Eriochrom black T
indicator. Mix well. Solution should be wine red.
3. Rinse the buret three times with the EDTA disodium salt titrant.
4. Fill buret with the EDTA titrant.
5. Remove any air bubbles from the buret and bring level of titrant to 0.00 ml.
6. Titrate the contents of the Erlenmeyer flask with EDTA solution until red tint disappears.
The color will turn purple. Continue titration slowly until the solution turns blue, which is
the endpoint. Record the volume of EDTA used.
7. Perform this titrant check two more times.
8. Calculate the normality of the EDTA as follows:
NormalityEDTA = (0.02 × S)/V(21.7)

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where
0.02 = prepared normality of EDTA.
S = volume of titrated CaCO3 solution (ml).
V = volume of EDTA used for titration.
Determine the normality with three parallel titrations. The exact normality is calculated by averag-
ing the three results.
18.9.2.3 Procedure
1. Measure a 100-ml sample or portion diluted to 100 ml into a 250-ml Erlenmeyer flask.
2. Add 5 ml of buffer solution and a scoopful of Eriochrom black T indicator and mix.
Solution should be wine red.
3. Rinse the buret with standardized EDTA titrant three times.
4. Fill buret with standardized EDTA titrant.
5. Remove air bubbles from the buret and check 0.00 level.
6. Titrate sample until red tint disappears. The color should turn pink. Continue titration
slowly until the solution turns blue.
7. If the volume of the titrant used is over 25 ml, repeat titration by using a smaller sample
size or appropriate dilution.
mg/l hardness as CaCO3 = (V − B) × N × 50 × 1000/SV (18.1)
where
V = volume of titrant used for sample (ml).
B = volume of titrant used for blank (ml).
N = the determined normality of EDTA.
50 = equivalent weight of CaCO3 (100/2).
SV = sample volume (ml).
Use appropriate dilution factor as necessary.

18.9.2.4.1 Total Hardness Calculation
mg/l hardness as CaCO3 = 2.497 (Ca mg/l) + 4.118 (Mg mg/l)
or
mg/l hardness as CaCO3 = [(Ca, mg/l)/0.4] + [(Mg, mg/l)/0.24]
For example, calcium and magnesium have been determined by the atomic absorption technique with
the following results:
Ca = 16 mg/l
Mg = 9.6 mg/l
Calculated total hardness value as CaCO3 is:
(2.497 × 16) + (4.118 × 9.6) = 79.5 mg/l

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or
(16/0.4) + (9.6/0.24) = 80 mg/l
18.9.3 CALCIUM DETERMINATION BY EDTA TITRIMETRIC METHOD

When EDTA is added to water containing both calcium and magnesium, it combines first with calcium.
Calcium can be determined directly with EDTA when the pH is made sufficiently high so that the mag-
nesium is largely precipitated as the hydroxide and an indicator is used that combines with calcium only.
18.9.3.1 Apparatus and Materials

Apparatus and materials are the same as those listed for total hardness determination (Section
18.9.2.1).
18.9.3.2 Reagents
18.9.3.2.1 Sodium Hydroxide, NaOH, 1N

Place a 2-liter beaker or Erlenmeyer flask on a magnetic stirrer under a laboratory hood. Add about
500 ml of DI water and a magnetic stirring bar and add 40 g of NaOH slowly to the water while stir-
ring.
Caution: This reaction liberates heat! After complete dissolution, transfer into a 1-liter volumetric
flask and fill up to the mark with DI water. Mix well. Store in polyethylene bottle.
18.9.3.2.2 Murexide (Ammonium Purpurate) Indicator
A ground mixture of dye powder and sodium chloride provides a stable form of the indicator. Weigh
0.200 g of murexide (ammonium purpurate) and 100 g NaCl, and grind the mixture to 40 to 50 mesh
in a porcelain mortar or in a coffee grinder used for this purpose.
18.9.3.2.3 Standard EDTA Titrant, 0.02N
Prepare as described in Section 18.9.2.2.3.
1 ml = 400.8 µg Ca
18.9.3.2.4 Reference Stock Solution, 12,500 mg/l Ca as CaCO3

Prepare as described in Section 18.9.2.2.5 with a value of 12,5018 mg/l of Ca as CaCO3.
18.9.3.2.5 Reference Standard Solution, 62.5 mg/l
Pipet 5 ml of reference stock solution (Section 18.9.3.2.4) into a 1-liter volumetric flask and dilute
to the required volume with DI water.
18.9.3.3 Procedure
1. Measure 100-ml sample or smaller portion diluted to 100 ml.
2. Add 2 ml of 1N NaOH solution or a volume sufficient to produce a pH of 12 to 13. Stir.
3. Add a scoopful of indicator. The color of the sample becomes pink.
4. Titrate with standardized EDTA solution until the pink color changes to purple, which is
the endpoint. Titrate immediately after adding indicator because the solution is unstable
under alkaline conditions.
5. Check endpoint by adding one to two drops of titrant in excess to make certain that no fur-
ther color change occurs. Facilitate endpoint recognition by preparing a color-comparison
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blank containing 2 ml of 1N NaOH and a scoopful of indicator powder and sufficient

EDTA titrant (0.05 to 0.10 ml) to produce an unchanging color.
Calcium as CaCO3 = (ml × N × 50 × 1000)/ml sample (18.2)
where
ml = ml of ETA standard used for titration.
N = exact normality of the EDTA titrant.
50 = equivalent weight of CaCO3.
Calcium as Ca (mg/l) = Ca as CaCO3 (mg/l) × 0.4 (18.3)
Magnesium may be estimated based on the difference between total hardness and calcium
as CaCO3:
Mg as CaCO3 (mg/l) = total hardness as CaCO3 (mg/l) − calcium as CaCO3 (mg/l)
Magnesium as Mg (mg/l) = magnesium as CaCO3 (mg/l) × 0.24 (18.4)
18.10 CHROMIUM
Chromium salts are used extensively in industrial processes and may enter a water supply through
waste discharge. Chromate compounds frequently are added to cooling water for corrosion control.
Chromium may exist in water supplies in both the hexavalent and the trivalent states, although the
trivalent form rarely occurs in potable water.
Selection of method: Use the colorimetric method for the determination of hexavalent chromium
in natural or treated water intended to be potable. Use the GrAAS method for determination of low
levels of total chromium (less than 50 mg/l) in water and wastewater. Use the FAAS or ICP method
to measure concentrations up to the milligram per liter level.

If the sample contains a higher level of alkali metal content than the standards, ionization interfer-
ence may cause problems. To avoid this interference, add potassium-chloride, ionization-suppressant
solution to standards and samples.
Background correction may be required because nonspecific absorption and scattering can be
significant at the analytical wavelength. Background correction with certain instruments may be
difficult at this wavelength due to low-intensity output from hydrogen or deuterium lamps. Consult
the instrument manufacturer’s literature for details.

• Instrument: Chromium hollow cathode lamp
• Fuel: Acetylene
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For concentration of chromium below 0.2 mg/l, the furnace procedure is recommended.

Low concentrations of calcium and/or phosphate may cause interferences; at concentrations above
200 mg/l, calcium’s effect is constant and eliminates the effect of phosphate. Calcium nitrate is there-
fore added to ensure a known constant effect. Nitrogen should not be used as the purge gas because
of possible CN band interference.
Background correction may be required because nonspecific absorption and scattering can be
significant at the analytical wavelength. Background correction with certain instruments may be dif-
ficult at this wavelength due to low-intensity output from hydrogen or deuterium lamps. Consult the
instrument manufacturer’s literature for details.
Prepare calibration standards at the time of analysis. These standards should be prepared to con-
tain 0.5% (v/v) HNO3, 1 ml of 30% H2O2, and 1 ml of calcium nitrate solution (dissolve 11.8 g of cal-
cium nitrate (Ca(NO3)2.4H2O), and dilute to 1 liter with reagent-grade water).

• Purge gas: Argon (N should not be used!)

18.11 HEXAVALENT CHROMIUM

18.11.1 CHELATION/EXTRACTION METHOD
This method is suitable for determining the concentration of dissolved hexavalent chromium, Cr(VI)
in EP toxicity-characteristic extracts, groundwaters, and domestic and industrial wastes provided that
no interfering substances are present. The method is based on the chelation of hexavalent chromium
with ammonium pyrrolidine dithiocarbamate (APDC) and extraction with methyl isobutyl ketone
(MIBK). The extract is aspirated into the flame of an atomic absorption spectrophotometer.
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High concentrations of other metals may interfere. Because the stability of Cr(VI) is not com-
pletely understood, the chelation and extraction should be carried out as soon as possible. To retard
the chemical activity of hexavalent chromium, samples and should be stored at 4°C until analysis.
18.11.1.1 Reagents
18.11.1.1.1 Ammonium Pyrrolidine Dithiocarbamate (APDC) Solution
Dissolve 1.0 g of APDC and dilute to 100 ml with reagent-grade water. Prepare fresh daily.
18.11.1.1.2 Bromphenol Blue Indicator Solution
Dissolve 0.1 g of Bromphenol blue in 100 ml of 50% ethanol.
18.11.1.1.3 Potassium Dichromate Standard Solution I
Dissolve 0.2829 g of pure dried K2Cr2O7 and dilute to 1000 ml with reagent-grade water.
1 ml = 100 µg Cr
18.11.1.1.4 Potassium Dichromate Standard Solution II

Dilute 100 ml of potassium chromium standard I (Section 18.11.1.1.3) to 1 liter with reagent-grade
water.
1 ml = 10 µg Cr
18.11.1.1.5 Potassium Dichromate Standard Solution III

Dilute 10 ml of potassium dichromate standard II (Section 18.11.1.1.4) to 1 liter with reagent-grade
water.
1 ml = 0.10 µg Cr
18.11.1.1.6 Methyl Isobutyl Ketone (MIBK)

Avoid material that comes into contact with metal or metal-lined caps.
18.11.1.1.7 Sodium Hydroxide 1M Solution
Dissolve 40 g NaOH in reagent-grade water. Caution: Do not forget that the reaction of NaOH and
water liberates extreme heat! Make the dissolution slowly under a chemical hood. Cool and dilute to
1 liter with reagent-grade water.
18.11.1.1.8 Sulfuric Acid, 0.12M
Slowly add 6.5 ml of spectrograde-quality H2SO4 to reagent-grade water and dilute to 1 liter.
18.11.1.2 Procedure
1. Pipet a volume of sample containing less than 2.5 µg chromium (maximum 100 ml) into
a 200-ml volumetric flask and adjust the volume to approximately 100 ml.
2. Prepare a blank and sufficient standards, and adjust the volume of each to approximately
100 ml.
3. Add two drops of Bromphenol blue indicator solution (Section 18.11.1.1.2).
4. Adjust the pH by the addition of 1M NaOH (Section 18.11.1.1.7) by drops until a blue
color persists.
5. Add 0.12M H2SO4 (Section 18.11.1.1.8) dropwise until the blue color just disappears in
both the standards and sample. Then add 2.0 ml of 0.12M H2SO4 in excess. At this point,
pH should be 2.4.
6. Add 5.0 ml of APDC solution (Section 18.11.1.1.1) and mix. The pH should then be ap-
proximately 2.8.
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7. Add 10.0 ml of MIBK (Section 18.11.1.1.6) and shake vigorously for 3 min.
8. Allow the layers to separate and add reagent-grade water until the ketone layer is com-
pletely in the neck of the flask.
9. Aspirate the ketone layer and record the scale reading for each sample and standard against
the blank. Repeat and average the duplicate results.
10. Determine Cr concentration in milligrams per liter.
A working curve must be prepared with each set of samples.
18.11.1.3 Verification
• For every sample matrix analyzed, verification is required to ensure that neither a reduc-
ing condition nor chemical interference is affecting chelation. To verify the absence of in-
terference, the spike recovery must be between 85 and 115%.
• If addition of the spike extends the concentration beyond the calibration curve, the analy-
sis solution should be diluted with blank solution and the calculated results adjusted ac-
cordingly.
• If the result of verification indicates a suppressive interference, the sample should be di-
luted and reanalyzed. If the interference persists after sample dilution, an alternative
method should be used.
• Acidic extracts that yield recoveries of less than 85% should be retested to determine if the
low spike recovery is due to the presence of residual reducing agent. This determination
should be performed by first making an aliquot of the extract alkaline (8.0–8.5 pH) using
1N NaOH and then respiking and analyzing. If a spike recovery of 85 to 115% is obtained
in the alkaline aliquot of an acidic extract that initially was found to contain less than 5
mg/l Cr(VI), the analytical method has been verified.
18.11.1.4 Quality Control

Calibration curves must be composed of a minimum of a blank and three standards. A calibration
curve should be made for every hour of continuous sample analysis. Employ a minimum of one blank
per sample batch to determine whether contamination or memory effects are occurring.
Verify calibration with an independently prepared check standard every 15 samples. Run one
spike duplicate sample for every ten samples. A duplicate sample is a sample brought through the
entire sample preparation and analytical process. The standard additions method should be used for
the analysis of all EP extracts and when a new sample matrix is being analyzed.
18.11.2 COLORIMETRIC METHOD

Dissolved hexavalent chromium, in the absence of interfering amounts of substances such as molyb-
denum, vanadium, and mercury, may be determined colorimetrically by reaction with diphenylcar-
bazide in acid solution. A red-violet color of unknown composition is produced. The reaction is very
sensitive — the absorbancy index per gram atom of chromium is about 40,000 at 540 nm. Addition
of an excess of diphenylcarbazide yields the red-violet product, and its absorbance is measured pho-
tometrically at 540 nm.
Iron in concentrations greater than 1.0 mg/l may produce a yellow color, but the ferric iron color
is not strong and difficulty is not normally encountered if the absorbance is measured photometri-
cally at the appropriate wavelength.
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18.11.2.1 Reagents
18.11.2.1.1 Potassium Dichromate Stock Solution

Dissolve 141.4 mg of dried K2Cr2O7 in reagent-grade water and dilute to 1 l.
1 ml = 50 µg Cr
18.11.2.1.2 Potassium Dichromate Standard Solution

Dilute 10 ml of potassium dichromate stock solution (Section 18.11.2.1.1) to 100 ml.
1 ml = 5 µg Cr (5 mg/l)
18.11.2.1.3 H2SO4 10% (v/v)

Dilute 10 ml of spectrograde-quality H2SO4 to 100 ml with reagent-grade water.
18.11.2.1.4 Diphenylcarbazide Solution
Dissolve 250 mg 1,5-diphenylcarbazide in 50 ml of acetone. Store in brown bottle. Discard when the
solution becomes discolored.
18.11.2.1.5 Acetone (Analytical Reagent Grade)
Avoid material that comes in containers with metal or metal-lined caps.
18.11.2.2 Procedure
1. Collect samples as outlined in Section 14.5.4.
2. Transfer 95-ml sample to a 100-ml volumetric flask.
3. Add 2.0 ml of diphenylcarbazide solution (Section 18.11.2.1.4) and mix.
4. Add H2SO4 solution (Section 18.11.2.1.3) to obtain a pH of 2±0.5, dilute to 100 ml with
reagent-grade water, and let stand 10 min for full color development.
5. Measure absorbance at 540 nm against blank.
6. An aliquot of the sample containing all reagents except diphenylcarbazide should be pre-
pared and used to correct the sample.
7. From the corrected absorbance, determine the milligrams per liter of chromium present by
reference to the calibration curve for turbidity.
8. Prepare calibration curve to compensate for the possible slight losses of chromium during
digestion or other operations, and treat the chromium standards by the same procedure as
the sample. Prepare calibration standards from the potassium dichromate standard
solution (Section 18.11.2.1.2) in a concentration of 0.5 to 5.0 mg/l Cr(VI).
18.11.2.3 Quality Control

See chelation/extraction procedure in Section 18.11.1.
18.12 COBALT
Cobalt (Co) normally occurs at levels of less than 10 µg/l in natural waters. Wastewaters may con-
tain higher concentrations.
Selection of method: Use the FAAS (Chapter 8), GrAAS (Chapter 9), or ICP (Chapter 12) method.
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18.13 COPPER
Copper (Cu) salts are used in water supply systems to control biological growth in reservoirs and dis-
tribution pipes and to catalyze the oxidation of manganese. Corrosion of copper-containing alloys in
pipe fittings may introduce measurable amounts of copper into the water in a pipe system. Copper is
essential to humans; the adult daily requirement has been estimated at 2.0 mg.
Selection of method: FAAS, GrAAS, and ICP are recommended (see Chapters 8, 9, and 12, re-
spectively), because of their freedom from interferences.

Background correction may be required because nonspecific absorption and scattering can be sig-
nificant at the analytical wavelength. Background correction with certain instruments may be diffi-
cult at this wavelength due to low-intensity output from hydrogen or deuterium lamps. Consult the
instrument manufacturer’s literature for details.

• Instrument: Copper hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air
• Background correction: Recommended, if possible

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18.14 IRON
Iron (Fe) in water can cause staining of laundry and porcelain. Under reducing conditions, iron ex-
ists in the ferrous state. In the absence of complex-forming ions, ferric iron is not significantly solu-
ble unless the pH is very low. On exposure to air or addition of oxidants, ferrous iron is oxidized to
the ferric state and may hydrolyze to form insoluble, hydrated ferric oxide. In water samples, iron
may occur in true solution, in a colloidal state that may be peptized by organic matter, in inorganic
or organic iron complexes, or in suspended particles. It may be ferrous or ferric, or suspended or dis-
solved. Silt and clay in suspension may contain acid-soluble iron. Oxide particles are sometimes col-
lected with a water sample as a result of flaking of rust from pipes. Iron from a metal cap used to
close the sample bottle may contaminate the sample.
Selection of method: Sensitivity and detection limits for the FAAS procedure, the ICP method are
similar and generally adequate for analysis of natural or treated waters.

Iron is a universal contaminant, and great care should be taken to avoid contamination.

• Instrument: Iron hollow cathode lamp
• Wavelength: 248.3 nm (primary); 248.7, 248.8, 271.9, 302.1, 252.7, or 372.0 nm (alter-
nates)
• Fuel: Acetylene
• Oxidant: Air


Background correction is recommended. Nitrogen may also be used as the purge gas.


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18.15 LEAD
Lead (Pb) is a serious cumulative body poison. Natural waters seldom contain more than 5 µg/l, al-
though much higher values have been reported. Lead in a water supply may come from industrial,
mining, and smelter discharges or from the dissolution of old lead plumbing. Tap waters that are soft,
acid, and not suitably treated may contain lead resulting from an attack on lead service pipes or sol-
der pipe joints.
Selection of method: FAAS has a relatively high detection limit and requires an extraction pro-
cedure for the low concentrations common in potable water. The GrAAS method is much more sen-
sitive for low concentrations and thus does not require extraction. The ICP method has a sensitivity
similar to that of FAAS method.

• Instrument: Lead hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air

For concentrations of lead below 0.2 mg/l, the furnace technique is recommended.

If poor recoveries are obtained, a matrix modifier may be necessary. Add 10 µl of phosphoric acid to
1 ml of prepared sample in the furnace sampler cup and mix well.

atomization temperature for shorter time periods than the recommended settings above.

• Optimum concentration range: 5 to 100 µg/l
• Detection limit: 1 µg/l
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18.16 LITHIUM
A minor constituent of minerals, lithium (Li) is present in fresh waters in concentrations below 0.2
mg/l. Brines and thermal waters may contain higher lithium levels. The use of lithium or its salts in
dehumidifying units, medical waters, and metallurgical processes and the manufacture of some types
of glass and storage batteries may contribute to its presence in wastes. Lithium hypochlorite is avail-
able commercially as a source of chlorine and is used in swimming pools.
Selection of methods: FAAS (Chapter 8) and ICP (Chapter 12) methods are preferred.
18.17 MAGNESIUM
All elements forming stable oxyanions will complex magnesium and interfere unless lanthanum is
added. Addition of lanthanum to prepared samples rarely presents a problem because virtually all en-
vironmental samples contain sufficient magnesium to require dilution to be in the linear range of the
analytical method.
Calibration standards should be prepared by using the same type of acid and at the same con-
centration as will result in the sample to be analyzed after processing, including 1 ml of lanthanum
solution per 10 ml of solution. To prepare lanthanum chloride solution, dissolve 29 g of La2O3 in 250
ml of concentrated HCl. Caution: Reaction is violent! Dilute to 500 ml with reagent-grade water.
Selection of methods: Direct determination can be made with the FAAS (Chapter 8) and ICP
(Chapter 12) methods.

• Instrument: Magnesium hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air

• Optimum concentration range: 0.02 to 0.05 mg/l
18.18 MANGANESE
Although manganese (Mn) in ground water is usually present in the soluble divalent ionic form be-
cause of the absence of oxygen, part of or all manganese at a water treatment plant is in higher va-
lence states. Excess manganese in higher oxidation states must be detected with great sensitivity to
control treatment and prevent discharge into a distribution system. Although rarely present in excess
of 1 mg/l, manganese causes tenacious stains in laundry and plumbing fixtures. The low manganese
limits imposed on an acceptable water stem from these, rather than toxicological, considerations.
Special means of removal are necessary, such as chemical precipitation, pH adjustment, aeration, and
use of special ion-exchange materials. Manganese occurs in domestic wastewaters, industrial efflu-
ent, and receiving streams.
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Selection of method: FAAS, GrAAS, and ICP methods permit direct determination with accept-
able sensitivity.

• Instrument: Manganese hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air
• Type of flame: Slightly oxidizing (slightly lean fuel, stoichiometric)


The use of background correction is recommended. Nitrogen may also be used as purge gas.


18.19 MERCURY
Organic and inorganic mercury (Hg) salts are very toxic and their presence in the environment, es-
pecially in water, should be monitored.
Selection of method: The cold-vapor atomic absorption method should be used for all types of
samples.
18.19.1 COLD-VAPOR ATOMIC ABSORPTION TECHNIQUE

For both liquid and solid samples, see Section 10.3.5.
18.20 MOLYBDENUM
Molybdenum (Mo) occurs in trace levels (<10 µg/l) in natural waters. In waters draining mineralized
areas or in wastewaters from processes using Mo, concentrations maybe much higher.
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Selection of methods: The FAAS, GrAAS, or ICP method can be used, as described in Chapters
8, 9, and 12, respectively.

Interferences in an air–acetylene flame from Ca, Sr, SO4, and Fe are severe. These interferences are
greatly reduced in the nitrous oxide flame and by addition of 1 mg/l of aluminum to samples and stan-
dards. The calibration standards should be prepared using the same type of acid and at the same con-
centration as will result in the sample to be analyzed after processing. To each 100 ml of sample and
standard alike, add 2 ml of aluminum nitrate solution. (To prepare aluminum nitrate solution, dis-
solve 139 g of Al(NO3)3.9H2O in 150 ml of reagent-grade water, and heat to effect solution. Allow to
cool and make up to 200 ml.)

• Instrument: Molybdenum hollow cathode lamp
• Fuel: Acetylene

For concentrations of molybdenum below 0.2 mg/l, the furnace technique is recommended.

Molybdenum is prone to carbide formation. Use a pyrolytically coated graphite tube. Memory effects
are possible, and cleaning of the furnace may be required after analysis of highly concentrated sam-
ples or standards.

• Purge gas: Argon (N should not be used!)
based on the use of a 20-µl injection, continuous-flow purge gas.

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18.21 NICKEL
Selection of method: The FAAS and ICP methods are preferred for all types of samples.

High concentrations of Fe, Co, or Cr may interfere, requiring either matrix matching or use of a ni-
trous oxide–acetylene flame. A nonresonance line of Ni at 232.14 nm causes nonlinear calibration
curves at moderate to high Ni concentrations, requiring sample dilution or use of the 352.4 nm line.

• Instrument: Nickel hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air


Background correction is recommended. Nitrogen may also be used as the purge gas.


18.22 POTASSIUM
Potassium (K) ranks seventh among the elements in order of abundance, yet its concentration in most
drinking waters seldom reaches 20 mg/l. Occasionally, brines may contain more than 100 mg/l.
Selection of method: The FAAS and ICP methods are acceptable.

In air–acetylene or other high-temperature flames (>2800°C), potassium can experience partial ion-
ization, which indirectly affects absorption sensitivity. The presence of other alkali salts in the
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sample can reduce ionization and thereby enhance analytical results. The ionization-suppressive ef-
fect of sodium is small if the ratio of Na to K is under 10. Enhancement due to sodium can be stabi-
lized by adding excess sodium (1000 µg/ml) to both sample and standard solutions. If more stringent
control of ionization is required, the addition of cesium should be considered. Reagent blanks should
be analyzed to correct for potassium impurities in the buffer stock.

• Instrument: Potassium hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air
• Type of flame: Slightly oxidizing (lean fuel)

• Optimum concentration range: 0.02 mg/l
18.23 SELENIUM
Selenium (Se) is an essential trace nutrient, and selenium-deficiency diseases are well known in vet-
erinary medicine. Above trace levels, ingested selenium is toxic to animals and may be toxic to hu-
mans. The selenium concentration in most drinking waters and natural waters is less than 10 µg/l.
However, the pore water in seleniferous soils in semiarid areas may contain up to hundreds of mi-
crograms of selenium per liter. Certain plants that grow in such areas accumulate large concentra-
tions of selenium and may poison livestock that graze on them. Water drained from such soil may
cause severe environmental pollution and wildlife toxicity. Soluble selenium can leach from coal ash
at electric power plants that burn seleniferous coal. Selenium derives from microbial degradation of
seleniferous organic matter. Nonvolatile organic selenium compounds may be released in water by
microbial processes.
Selection of method: Selenium can be determined by the hydride-generation atomic absorption
spectrometric or GrAAS methods. For higher concentrations of selenium, the ICP method may be
used.

Prior to analysis, samples must be prepared in order to convert organic forms of selenium to inor-
ganic forms, minimize organic interferences, and convert samples to suitable solutions for analysis.
Elemental selenium and many of its compounds are volatile; therefore, samples may be subject to
losses of selenium during sample preparation. Spike samples and relevant standard reference mate-
rials should be processed to determine if the chosen dissolution method is appropriate.
Caution must be taken during the selection of temperature and times for the dry and char (ash)
cycles. A nickel-nitrate solution must be added to all digestates prior to analysis to minimize
volatilization losses during drying and ashing.
Selenium analysis can suffer from severe nonspecific absorption and light scattering caused by
matrix components during atomization. Selenium analysis is particularly susceptible to these prob-
lems because of its low analytical wavelength. Simultaneous background correction is required to
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avoid erroneous high results. High iron levels can produce overcorrection in a deuterium background.
Zeeman background correction can be useful in this situation.
If the analyte is not completely volatilized and removed from the furnace during atomization,
memory effects will occur. If this situation is detected, the tube should be clean by operating the fur-
nace at full power at regular intervals in the analytical scales.
Selenium analysis suffers interference from chlorides (>800 mg/l) and sulfate (>200 mg/l). The
addition of nickel nitrate such that the final concentration is 1% nickel will reduce this interference.
18.23.1.1 Reagents
18.23.1.1.1 Concentrated HNO3
The reagent is commercially available.
18.23.1.1.2 30% H2O2
The reagent is commercially available.
18.23.1.1.3 Nickel-Nitrate Solution 5%
Dissolve 24.780 g of Ni(NO3)2.6H2O in reagent-grade water and dilute to 100 ml.
18.23.1.1.4 Nickel Nitrate Solution 1%
Dissolve 20 ml of the 5% nickel-nitrate solution (Section 18.23.1.1.3) to 100 ml with reagent-
grade water.
18.23.1.1.5 Selenium Calibration Standards
Withdraw an appropriate aliquot of the stock solution (1000 mg/l) and add 1 ml of concentrated
HNO3, 2 ml of 30% H2O2, and 2 ml of 5% nickel-nitrate solution. Dilute to 100 ml with reagent-
grade water.
18.23.1.2 Procedure
1. Transfer 100 ml of well-mixed sample to a 250-ml Griffin beaker; add 2 ml of 30% H2O2
and sufficient concentrated HNO3 to result in an acid concentration of 1% (v/v).
2. Heat for 1 h at 95°C or until the volume is slightly less than 50 ml.
3. Cool and bring back to 50 ml with reagent-grade water.
4. Pipet 5 ml of this digested solution to a 10-ml volumetric flask, add 1 ml of the 1% nickel-
nitrate solution, and dilute to 10 ml with reagent-grade water.
5. The sample is ready now for injection into the furnace. Furnace parameters suggested by
the manufacturer should be employed as guidelines.
6. Inject a measured microgram-per-liter aliquot of sample into the furnace and atomize. The
use of multiple injections can improve accuracy. Run a check standard after every ten sam-
ples. Standards are run in part to monitor the life and performance of the graphite tube.
Lack of reproducibility or significant change in the signal for the standard indicates that
the tube should be replaced.
7. Duplicates, spiked samples, and check standards should be analyzed every 20 samples.


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18.23.2 ATOMIC ABSORPTION GASEOUS HYDRIDE TECHNIQUE

See Chapter 11 for instrumentation and procedure details.
18.24 SILVER
The silver (Ag) concentration in drinking waters varies from 0 to 2 µg/l, with a mean of 0.13 µg/l.
Silver can cause argyria, a blue-gray discoloration of the skin and eyes. Concentrations in the range
of 0.4 to 1 mg/l have caused pathological changes in the kidneys, liver, and spleen of rats. Toxic ef-
fects in freshwater fish have been observed at concentrations as low as 0.17 µg/l. Relatively small
quantities of silver are bactericidal or bacteriostatic and are sometimes used in disinfecting swim-
ming pool waters.
Selection of method: The FAAS and ICP methods are preferred. The GrAAS method is the
most sensitive.

Background correction is required because nonspecific absorption and light scattering may occur at
the analytical wavelength. Silver nitrate solutions are light sensitive and tend to plate out on container
walls. Silver standards should be stored in brown bottles. Silver chloride is insoluble; therefore, HCl
should be avoided.

• Instrument: Silver hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air
• Type of flame: Oxidizing


Background correction may be required if the sample contains highly dissolved solids. The use of
halide acids should be avoided.

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• Detection limit: 0.2 µg/l
18.25 SODIUM
Sodium (Na) ranks sixth among the elements in order of abundance and is present in most natural
waters. Levels may vary from less than 1 mg/l to more than 500 mg/l. Relatively high levels may be
found in brines and hard waters softened by the sodium exchange process. The ratio of sodium to
total cations is important in agriculture and human pathology. A limiting concentration of 2 to 3 mg/l
is recommended in feed waters destined for high-pressure boilers.
Selection of method: The FAAS or ICP method is recommended.

Ionization interferences can affect analysis for sodium; therefore, samples and standards must be ma-
trix matched or an ionization suppressant employed. Sodium is a universal contaminant, and great
care should be taken to avoid contamination.

• Instrument: Sodium hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air

18.26 THALLIUM
Thallium (Ta) occurs normally at trace levels (<10 µg/l) in natural waters. Because thallium is toxic,
it has been placed on several regulatory lists.
Selection of method: Use the FAAS method (Chapter 8) or the ICP method (Chapter 12).

Background correction is required. HCl should not be used.

• Instrument: Thallium hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air
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The use of background correction is recommended. Nitrogen may also be used as the purge gas.

Other operation parameters should be set as specified by the instrument manufacturer.

18.27 TIN
Tin (Sn) is normally soluble only at trace levels in natural waters (<100 µg/l), except in process waste
waters or mineral waters.
Selection of method: Use either the FAAS (Chapter 8) or GrAAS (Chapter 12) method.

• Instrument: Tin hollow cathode lamp
• Fuel: Acetylene

• Sensitivity: 4 mg/l
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The use of background correction is recommended. Nitrogen may also be used as a purge gas. Tin
analysis is sensitive to chloride concentration. If chloride concentration presents a matrix problem or
causes loss prior to atomization, add an excess of 5 mg of ammonium nitrate to the furnace and ash
using a ramp as necessary or with incremental steps until the recommended ashing temperature is
reached. Extended ashing times have been reported to improve precision.


18.28 VANADIUM
Vanadium (V) may play a beneficial role in the prevention of heart disease. The mean concentration
found in U.S. drinking waters is 6 µg/l.
Selection of method: The FAAS (Chapter 8) and ICP (Chapter 12) methods are recommended.

High concentrations of aluminum, titanium, or the presence of bismuth, chromium, cobalt, iron,
acetic acid, phosphoric acid, surfactants, detergents, or alkali metals, may interfere. The interference
can be controlled by adding 1000 mg/l aluminum to samples and standards.
The calibration standards should be prepared using the same type of acid and at the same con-
centration as will result in the sample to be analyzed after processing. In addition, 2 ml of the
aluminum nitrate solution should be added to each 100 ml of standards and samples. (To prepare the
aluminum nitrate solution, dissolve 139 g Al(NO3)3.9H2O in 150 ml of reagent-grade water; heat to
complete dissolution. Allow to cool and dilute to 200 ml with reagent-grade water.)

• Instrument: Vanadium hollow cathode lamp
• Fuel: Acetylene

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For concentrations of vanadium below 0.5 mg/l, the furnace technique is recommended.

Vanadium is refractory and prone to form carbides. Consequently, memory effects are common, and
care should be taken to clean the furnace before and after analysis. Nitrogen should not be used as a
purge gas.

• Purge gas: Argon (N should not be used)

18.29 ZINC
Zinc (Zn) is an essential and beneficial element in human growth. Concentrations above 5 mg/l can
cause a bitter astringent taste and an opalescence in alkaline waters. Zinc concentrations in U.S.
drinking waters range from 0.06 to 7.0 mg/l with a mean of 1.33 mg/l. Zinc most commonly enters
the domestic water supply from deterioration of galvanized iron and dezincification of brass. In such
cases, lead and cadmium may also be present because they are impurities of the zinc used in galva-
nizing. Zinc in water also may result from industrial waste pollution.
Selection of method: The FAAS (Chapter 8) and ICP (Chapter 12) methods are preferable.

High levels of silicon, copper, or phosphate may interfere. Addition of strontium (1500 mg/l) re-
moves the copper and phosphate interference.

• Instrument: Zinc hollow cathode lamp
• Fuel: Acetylene
• Oxidant: Air
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• Optimum concentration range: 0.2 to 4 µg/l
• Detection limit: 0.05 µg/l
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Laboratory Safety Rules

19
Before beginning any type of laboratory work, it is important to understand the potential hazards in
the laboratory, to be familiar with the precautions and rules, and to recognize and avoid the causes of
those hazards. According to the Occupational Safety and Health Act (OSHA), “[E]ach employer has
the general duty to furnish each of the employees a workplace free from recognized hazards causing
or likely to cause death or serious harm.” Comprehensive safety training is essential for all labora-
tory workers.
19.1 LABORATORY HAZARDS

Laboratory hazards can be categorized as chemical hazards, fire hazards, and careless habits.
19.1.1 CHEMICAL HAZARDS

Virtually all chemicals are toxic to some extent, and care should be taken in handling them. Chemical
hazards may be minimized by the following precautions.
19.1.1.1 Cleanliness
Cleanliness in the laboratory is essential:
• Wash hands periodically and immediately after contact with chemicals and just before
leaving the laboratory.
• Never drink from laboratory glassware.
• Keep work areas clean. Clean working areas before and after work.
• Use clean laboratory coats and aprons. These garments are designed to protect the body
from chemical spills. Dirty clothing can be a source of health hazards and contamination.
19.1.1.2 Eye Protection

The eyes are especially susceptible to injury from chemicals. Breakage of glass containers of acid,
bases, and other chemicals and out-of-control chemical reactions are the principal hazards. Safety
glasses, goggles, or face shields should be worn during laboratory work. In the event of chemical
spray in eyes, immediately flood the eyes with water using a specially designed eye-wash fountain
or quick flushing with water from the nearest tap, and seek medical attention as soon as possible.
19.1.1.3 Skin Contact with Certain Chemicals

Chemical burns can result from contact with strong acids or bases. Certain chemicals are absorbed
through the skin. Because many chemicals absorb rapidly through the skin, prompt clean-up is im-
portant. Remove contaminated clothing immediately and flush affected areas with a large quantity of
water. Medical attention may be necessary, depending on the amount of chemical involved.
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19.1.1.4 Body Protection

• Use laboratory coats or aprons. Laboratory coats are made from materials that provide
protection against acids and bases. Laboratory aprons are not affected by ordinary corro-
sive fluids or other chemicals.
• Never wear open-toe shoes or sandals. This type of footwear offers little or no protection
against chemical spills or broken glass.
• Secure ties or scarves with fasteners.
• Put long hair up and out of the way.
• When handling corrosive chemicals, use protective gloves. Protective gloves are selected
according to need. Asbestos gloves protect against heat, but they are not advisable for han-
dling corrosive chemicals (acids or bases), because asbestos absorbs the substance and in-
creases contact time and area. When working with hot objects or organic solvents, do not
use rubber or plastic gloves, because they may soften and dissolve.
19.1.1.5 Ingestion of Toxic Chemicals

Do not consume or store food or beverages in the laboratory. Food is easily contaminated, such as by
traces of chemicals on hands. To avoid any possibility of ingesting chemical solutions while using a
pipet, use a pipeting bulb and not the mouth.
19.1.1.6 Inhalation of Volatile Liquids and Gases

The presence of these substances in the air (even in low concentrations) is hazardous. Acute expo-
sure to extremely high concentrations in vapors (above the maximum allowable concentration) can
cause unconsciousness and even death, if the person is not removed from the area and if medical at-
tention is delayed. The exposure to solvent and chemical vapors can be avoided by working with such
chemicals under chemical hoods and wearing protective respiratory devices. Good ventilation is es-
sential to a safe laboratory.
19.1.1.6.1 Toxicity of Metallic Elements
Metals with a specific gravity of greater than 5 are called heavy metals. In the metallic state they are
harmless, but in the vapor state these elements and their soluble compounds are toxic. The most com-
mon heavy metals are antimony (Sb), arsenic (As), cadmium (Cd), chromium (Cr), lead (Pb), mer-
cury (Hg), nickel (Ni), silver (Ag), and thallium (Tl).
19.1.1.6.2 Chemical Dust
Fine-powder chemicals can be inhaled as dust; therefore, these chemicals should also be handled
under a laboratory hood.
19.1.1.7 Chemical Spills

19.1.1.7.1 Solid, Dry Substances
Spills of chemicals in this form can be swept together, brushed into a dustpan or cardboard recepta-
cle, and then deposited in an appropriate waste container.
19.1.1.7.2 Acid Spills
Clean up acid spills by using the appropriate spill kit and following the instructions. The material in
such kits neutralizes and absorbs the acid for easy clean-up. Afterwards the area should be washed
with water. Alternatively, use soda ash (Na2CO3) or sodium bicarbonate (NaHCO3) solution for neu-
tralization, and then flush the area with water.
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Laboratory Safety Rules 307
Caution: When water is poured on spills of concentrated sulfuric acid (H2SO4), tremendous heat
is released (exothermic reaction) and the acid splatters. Deluge with water to dilute the acid to min-
imize heat generation and splattering.
19.1.1.7.3 Alkaline Spills
Alkaline spills are treated similarly to acid spills; use an alkaline spill kit. Alternatively, use a weak
acid solution, such as diluted acetic acid, for neutralization. The area should then be flushed with
water to a floor drain. If a mop and bucket are used, flush by replacing water frequently.
Caution: Alkali solutions make the floor slippery!
Clean sand can also be used to clean up alkaline spills. Throw sand over the spill and sweep up.
The wet sand is then discarded.
19.1.1.7.4 Volatile Solvent Spills
Volatile solvents evaporate very rapidly because of the extremely large surface area. This kind of the
spill can create a fire hazard if the solvent is flammable and will invariably cause highly dangerous
concentrations of fumes in the laboratory. When inhaled, these fumes cause serious injuries. They
may also become explosive upon mixing with air.
To clean up a small spill, wipe up the liquid with absorbent cloths or towels and discard them in
an appropriate waste receptacle. If a large amount of solvent is involved in the spill, use a mop and
pail. Squeeze out the mop in the pail and continue as needed.
19.1.1.7.5 Oily Substance Spills
This type of spill should be cleaned up with an appropriate nonflammable volatile solvent. Pour sol-
vent on an absorbent cloth, and wipe up the spilled substance. Rinse the cloth in a pail of solvent to
remove all spilled material, because oily floors are slippery and dangerous. Finally, thoroughly scrub
with detergent and water to remove oily residue.
19.1.1.7.6 Mercury Spills
Spills are one of the most common sources of mercury vapor in laboratory air. In a spill, mercury may
be distributed over a wide area, exposing a large surface area of the metal, and droplets become
trapped in crevices. Unless the laboratory has adequate ventilation, mercury vapor concentration (ac-
cumulated over time) may exceed the recommended limit. Vibration increases mercury vaporization.
Caution: Surfaces that appear to be free of mercury will harbor microscopic droplets.
To clean up mercury spills, push droplets together to form pools, and then use a suction device
to pick up the mercury. If there are cervices or cracks in the floor that can trap small droplets of mer-
cury that cannot be picked up, seal over the cracks with a thick covering of floor wax or an aerosol
hair spray. The covering will dramatically reduce vaporization. Sulfur powder can also be used to fix
mercury. Mercury spill kits are also available for proper mercury clean-up.
19.1.2 FIRE HAZARDS

Fire in a chemical laboratory can be dangerous and devastating. In case of fire, stay calm and think!
Sources of fires include electrical equipment, friction, mechanical sparks, flames, hot surfaces, and
flammable organic compounds. Accidental ignition of volatile organic solvents is perhaps the most
common source of laboratory fires. To avoid accidental spills and reduce fire hazards, keep volatile
solvents in small containers and never work with a volatile solvent around an open flame. The sooner
you respond to put out a fire, the easier it is to control.
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19.1.2.1 Fire Classifications

The appropriate response to a fire depends on the type of material being consumed. The use of the
wrong type of firefighting equipment may increase the intensity of the fire. Fire classifications are
described below.
19.1.2.1.1 Class A Fires
These fires are caused by the burning of paper, wood, and textiles. Almost any type of extinguisher
is satisfactory.
19.1.2.1.2 Class B Fires
This type of fire is caused by the burning of oil, grease, organic solvents, and paint. Use a dry-chem-
ical, liquid, CO2, or foam extinguisher.
19.1.2.1.3 Class C Fires
This type consists of electrical fires in equipment. Do not use a water or foam extinguisher, because
you may become a part of the electrical circuit and be electrocuted! Use a CO2 or dry-chemical fire
extinguisher only.
19.1.2.1.4 Class D Fires
Class “D” fires are caused by sodium, potassium, magnesium, lithium, and all metal hydrides. Use a
dry, soda-ash fire extinguisher, sodium chloride, or dry sand.
19.1.2.2 Fire-Fighting Responses

19.1.2.2.1 Fire in Clothing
Wrap the person in a fire blanket or heavy towels. Use an emergency shower.
19.1.2.2.2 General Fires
Select the proper fire extinguisher according to the type of fire. First, cool the area around the fire
with the extinguisher to prevent the fire from spreading. Next, use the extinguisher at the core area
of the fire. Finally, extinguish scattered remnants of the fire.
19.1.2.2.3 Electrical Fires
First, disconnect the apparatus by pulling the safety switch to avoid the possibility of being electro-
cuted. Then, use class C (CO2 or dry chemical) extinguisher.
19.1.2.2.4 Poisonous Gas Fires
Use an appropriate respirator, and select the proper fire extinguisher. If the fire gets beyond the con-
trol of the available fire extinguisher, get out of the room immediately. Close the door to prevent
drafts and gas spread. Always be certain that no one is left behind.
In case of fire, immediately notify the local fire department!
19.1.3 CARELESSNESS
Most laboratory accidents are caused by impulsive acts that later seem thoughtless, careless, and even
reckless. Thus, always think about the possible consequences of your actions before you act.
19.1.3.1 Hazards from Falling Objects

Falling objects can cause serious injuries. Do not place heavy objects on high shelves! If a heavy ob-
ject must be placed on a shelf, secure it with a belt or chain. Be careful when moving heavy instru-
ments and other heavy objects; use a laboratory cart whenever possible.
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19.1.3.2 Hazards from Falling

Never climb on drums, cartons, or boxes to reach objects located on high shelves. You may be se-
verely injured, and the injury can be compounded by breakage of glassware or chemical splash.
Always use a safety stepladder; special locking devices ensure that the rubber-tipped legs do not
move.
19.1.3.3 Transporting Large Bottles

Moving large bottles and carboys is a dangerous operation because of the potential for bottle break-
age and liquid spillage. Always use safety carts and safety bottle carriers when transporting large bot-
tles of chemicals. Safety bottle carriers prevent shock and breakage.
19.2 SAFE HANDLING OF COMPRESSED GASES

Cylinders of compressed gas can be dangerous because gases are contained under very high pressure.
Always follow safety precautions when handling such cylinders.
19.2.1 GENERAL PRECAUTIONS WHEN WORKING WITH COMPRESSED GASES

19.2.1.1 General Precautions
• Close off main cylinder valve when not in use.
• Close needle valve or auxiliary cut-off valve in the line and the cylinder. Do not rely solely
on the cylinder valve.
• Replace cylinders within reasonable time periods. Corrosive gas cylinders should be re-
placed every 3 months or less.
• Always use gases in areas where adequate ventilation is provided.
• Keep cylinders in outside storage, or use manifolds that pipe low-pressure gas into buildings.
• Use the smallest cylinder that is practical for the purpose.
19.2.1.2 Safety Rules for Using Compressed Gases

• Cylinder contents must be properly identified: Do not use cylinders without written con-
tent identification. Do not rely on color codes for identification. Do not destroy identifi-
cation tags or labels.
• Protect cylinder valves. Use only cylinders equipped with protective valve caps. Leave
caps in place until ready to use the gas.
• Store properly. Provide specifically assigned locations for cylinder storage, preferably in
a dry, fire-resistant, and well-ventilated area away from sources of ignition or heat.
Outdoor storage areas should have proper drainage and be protected from direct sunlight.
Secure cylinders by chains or other means to prevent accidental tipping or falling..
• Transport correctly. Transport cylinders by means of a suitable hand truck. Do not roll
cylinders on the ground!
• Do not drop. Never drop cylinders or permit them to strike each other.
• Return in condition received. Close valve, and replace cylinder-valve protective cap and
dust cap. Mark or label cylinder “EMPTY” or “MT.”
• Prevent confusing empties with full cylinders: Store empty cylinders in an area separate
from full cylinders. Connecting an empty cylinder to a pressurized system could cause
contamination or violent reaction in the cylinder.
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19.2.2 HAZARDOUS PROPERTIES OF COMPRESSED GASES

The properties of a compressed gas must be well known and understood before the gas is put to use.
Hazards include flammability, toxicity, and corrosivity.
19.3 STOCKROOM SAFETY RULES

The laboratory stockroom should be adequate and efficiently planned for safe operation.
19.3.1 SAFETY CHECKLIST FOR STORAGE ROOMS: Room Characteristics and

Organization
• Wide aisles, adequate lighting, and no blind alleys; the entire complex should be orderly
and clean
• Adequate ventilation and emergency exhaust system
• Well-marked exits, including emergency exits
• Adequate fire-protection and firefighting equipment
• Heavy items stored near the floor
• Proper storage for glass apparatus and tubing (never projecting beyond shelf limits)
• Fragile and bulky equipment secured to shelving.
• Shelving fitted with ledges to prevent items from sliding or rolling off
• Appropriate grouping and separation of liquids and hazardous chemicals
• No waste accumulation of any kind
• Safety ladders available; all laboratory personnel should be encouraged to use safety lad-
ders, because they prevent accidents and save time and effort
• No excessive heat, because of fire hazard
• Regular housekeeping activities aimed at maintaining safe storage practices
19.3.2 CHEMICAL STORAGE

Chemicals are manufactured in varying degrees of purity. Carefully select the grade of the chemical
that meets the need of the work to be done. Always recheck the label of the chemical that you are
using! The use of a wrong chemical can cause an explosion or ruin the analytical work. Carefully
check the information on the chemical container, including name, formula, formula weight, percent
impurities, analytical grade, health hazards, and safety codes.
19.3.2.1 Acids
Acids should be stored in original containers in cabinets labeled “Acids” and grouped by safety color
codes. Bottles with impact-resistant plastic coatings are preferred.
19.3.2.2 Flammable Solvents

Store these chemicals in original containers, in cabinets labeled “Flammable.” Large quantities
should be stored in metal safety cans outside of the laboratory in an area marked “Flammable
Storage Area.”
19.3.2.3 Solvents
Solvents should be stored in original containers in a separate cabinet labeled “Solvents” and in a well-
ventilated area.
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19.3.2.4 Chemicals Used in Volatile Organic (VOC) Analysis

These chemicals should be stored in original containers in a separate, appropriately labeled cabinet
and in a well-ventilated area. No other chemicals should be stored along with them.
19.3.2.5 Storage Organization

Chemicals should be stored in alphabetical order in the storage room, with records of date of arrival
and date of opening affixed to each container. Store phenol and hydrogen peroxide in a refrigerator la-
beled with “Chemical Storage.” The LabGuard Safety Label System on chemical bottles assists in the
proper storage of chemicals. Each chemical used in the laboratory should be accompanied by a
Material Safety Data Sheet (MSDS). MSDSs contain ingredients, physical and chemical characteris-
tics of the substance, physical hazards, reactivity and health hazards involved, and safe handling and
safety precautions. In addition, control measures to reduce harmful exposures are also listed in every
MSDS.
19.4 SUMMARY OF LABORATORY SAFETY RULES

1. Safety glasses/corrective glasses should be worn at all times in the laboratory. Visitors to
the laboratory must be appropriately warned and safety glasses made available to them.
2. Participation in practical jokes or “horseplay” in the laboratory is not permitted.
3. Each laboratory worker is expected to cooperate in keeping his or her working area in a
neat and orderly condition and to cooperate with others in keeping the entire laboratory
neat and orderly. A clean laboratory is a safe laboratory.
4. Proper techniques should be utilized when lifting, pushing, pulling, or carrying materials
to prevent injuries.
5. All laboratory personnel must know the location of fire extinguishers, safety showers, eye-
wash stations, and spill kits.
6. All laboratory workers must know how and when to use the equipment listed in item 5.
7. Eating, drinking, and smoking in the laboratory are never allowed. Never use laboratory
containers (beakers or flasks) for drinking.
8. No food or beverages intended for human consumption are stored in refrigerators in the
laboratory.
9. MSDSs must be attached to all chemicals used in the laboratory.
10. All chemicals should be clearly labeled. Do not use material from unlabeled containers.
Ensure that chemicals are clearly identified before using them.
11. In the event of chemical spraying in the eyes, use the eyewash station and report the inci-
dent to the laboratory supervisor.
12. Respirators must be used when working with hot acids or solvents that are handled when
not under a fume hood.
13. Pouring of volatile liquids should be done only in a well-ventilated hood remote from
sources of ignition.
14. Only minimum amounts of flammable liquids that are necessary for running a test should
be kept on workbenches.
15. Heavy reagent containers, such as 5-gallon containers, must not be carried or placed on a
shelf by one person working alone.
16. Face shields, rubber gloves, and protective rubber aprons should be used when preparing,
transporting, or pouring corrosive chemicals, such as concentrated acids and bases.
17. When diluting acid with water, always add the acid to the water, stirring constantly. Never
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add water to the acid, as this produces a violent reaction.

18. When drawing liquid into a pipet, always use a suction bulb. Mouth pipeting is never
allowed.
19. Pouring mercury into a sink or drain is strictly prohibited. Mercury will remain in the trap
and continue to vaporize and contaminate the air.
20. In the event of an acid spill on a person, flush thoroughly with water immediately.
Caution: Acid–water mixtures produce heat. Removal of clothing from the affected area while flush-
ing may be important so as not to trap hot acid–water mixtures against the skin. Acids or acid–water
mixtures can cause very serious burns if left in contact with skin for even a very short period of time.
21. Weak acids should be used to neutralize base spills, and weak bases should be used to neu-
tralize acid spills. Such solutions should be available in the laboratory in case of emer-
gency. Acid and base spill kits are also available.
22. Unsupervised or unauthorized work in the laboratory is not permitted.
23. Never wear open-toed shoes or sandals because they offer little or no protection against
chemical spills and broken glassware.
24. Keep ties and scarves secured with fasteners. Do not wear medallions, pendants, or other
hanging objects.
25. Tie long hair up and out of the way.
26. Asbestos gloves should be worn when handling or working with hot materials.
27. Gloves should be worn when exerting pressure is necessary to open jars, bottles, or other
containers.
28. A face shield should be worn when handling a receptacle containing more than 1 liter of
acid, alkali, or corrosive liquid.
29. Chemicals should never be transported, transferred, poured, or otherwise handled at a
height above one’s head.
30. Any injury, regardless of how superficial, should be reported to the laboratory supervisor
(or instructor in a school laboratory), and appropriate first-aid action taken.
31. A leakage check should be made on all gas lines and connections whenever a line is bro-
ken and reconnected.
32. Immediately report to the laboratory supervisor any failure of exhaust fans to evacuate va-
pors completely, defective electrical equipments, faulty or empty fire extinguishers, and
worn or defective rubber gas-burner hoses or other gas hazards.
33. Use a stepladder provided for this purpose when reaching into high shelving.
34. Never leave operations involving explosives or flammable mixtures unattended.
35. When transporting a large quantity of bottles, do so with a basket or receptacle designed
for this purpose.
36. Do not use damaged glassware.
37. Do not place glassware close to the edge of the laboratory bench; a passerby may knock
it off.
38. Wear goggles or a face shield when working with a glass apparatus that is under pressure
or vacuum.
39. When making a vacuum distillation, use a shield to guard to protect against explosion and
fire hazard.
40. Clean up broken glass immediately and place it in containers provided for broken glass.
Never dispose of broken glassware in a regular garbage container!
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Appendix A: Operation of Mass

Spectrophotometer
MASS SPECTROSCOPY
Mass spectroscopy is a technique used to determine relative atomic masses and the relative abundance
of isotopes, in chemical composition analysis and the study of ion reactions. In a mass spectrometer,
a sample (usually gaseous) is ionized and the positive ions produced are accelerated into a high-vac-
uum region containing electric and magnetic fields. These fields deflect and focus the ions onto a de-
tector. The fields can be varied in a controlled way so that ions of different types hit the detector.
OPERATION OF MASS SPECTROPHOTOMETER

1. All the air is pumped out of the instrument.
2. The sample (gaseous vapor of liquid or solid) is fed into the ionization chamber of the
spectrophotometer.
3. The sample is then exposed to a beam of rapidly moving electrons. When an accelerated
electron collides with an atom and knocks another electron out of it, the atom becomes a
positively charged ion.
4. The positive ions are accelerated out of the chamber by a strong electric field. Speeds at-
tained by the ions depend on their masses, with light ions reaching higher speeds than
heavy ones.
5. When the accelerated ions pass through a magnetic field generated by an electromagnet,
their paths are bent to an extent dependent on speed and hence on mass.
6. A signal is produced when the strength of the magnetic field is just enough to bend the
beam of ions so that they arrive at the detector.
7. The mass of the ion formed is then calculated based on the accelerating voltage and
strength of the magnetic field used to produce the signal.
The process of sample inlet system → Ionization chamber → Mass analyzer → Detector →
Signal A is shown in Figures A.1 and A.2, respectively.
MASS SPECTRUM
The mass spectrum obtained in the spectrophotometer signal consists of a series of peaks of variable
intensity to which mass/charge (m/e) values can be assigned. The mass spectrum is a plot of the de-
tector signal against the magnetic field. The positions of the peaks are used to calculate the mass of
accelerated ions, and the relative heights of the peaks indicate the proportions of ions of various
types. For organic molecules, the mass spectrum consists of a series of peaks, one corresponding to
the parent ion and the others to fragment ions produced in the ionization process. Molecule compo-
sition can be identified by characteristic patterns of lines.
313
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GAS CHROMATOGRAPHY–MASS SPECTROSCOPY (GC–MS)

Gas chromatography is used to separate a mixture into its components, which are then directly in-
jected into a mass spectrometer. The combined technique is known as gas chromatography–mass
spectroscopy (GC–MS).
FRACTIONAL ABUNDANCE OF ISOTOPES

In 1913, J.J. Thomson determined that the mass of neon is 20 amu, but he also found a less abundant
mass of 22 amu, which he thought was a contaminant. Later, with the benefit of improved equipment,
F.W. Aston showed that most elements are mixtures of isotopes. Isotopes are one or more atoms of the
same element that have the same number of protons in their nucleus but different numbers of neutrons.
FIGURE A.1 Diagram of a simple mass spectrophotometer showing separation of neon isotopes.
FIGURE A.2 Mass spectrophotometer. This instrument measures the mass of atoms and molecules.
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Appendix A: Operation of Mass Spectrometer 315
For instance, hydrogen isotopes include hydrogen (1 proton, no neutrons), deuterium (1 proton, 1 neu-
tron), and tritium (1 proton, 2 neutrons). Most elements in nature consist of a mixture of isotopes.
The mass spectrum provides all information necessary to calculate atomic weight: the mass of
each isotope and relative numbers, or fractional abundance of the isotopes. The fractional abundance
of an isotope is the fraction of the total number of atoms composed of a particular isotope. The atomic
weight of an element is calculated by multiplying each isotopic mass by its fractional abundance and
summing the values.
For example, positively charged neon atoms split into three beams corresponding to the three iso-
topes of neon. Each atom has a charge of +1 but has a mass number of 20, 21, or 22. Neon isotopes
and respective atomic mass units follow: neon 20, 19.992 amu; neon 21, 20.994 amu; and neon 22,
21.991 amu. Figure A.1 shows the mass spectrum of neon. The fractional abundance of the neon iso-
topes in naturally occurring neon follow: neon 20, 0.9051; neon 21, 0.0027; and neon 22, 0.0922. To
calculate the atomic weight of an element, multiply each isotope mass by its fractional abundance
and sum all values, as follows:
Isotope mass × Fractional abundance = Isotope atomic weight
Neon 20: 19.992 × 0.9051 = 18.O950
Neon 21: 20.994 × 0.0027 = 0.0567
Neon 22: 21.991 × 0.0922 = 2.0276
Element atomic weight = ∑ isotope atomic weight
Neon atomic weight: 18.0950 + 0.0567 + 2.0276 = 20.1793

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Appendix B: Silicon Chips

METALLIC CONDUCTION
In a metallic solid, cations lie in a regular array and are surrounded by a sea of electrons, as illustrated
in Figure 1.3. This structure gives unique properties to metals. One of the most striking properties of
a metal is its ability to conduct an electric current. The general term for this property is electronic con-
duction, and the specific term as applied to metals is metallic conduction. The ability of a substance
to conduct electricity is measured by its resistance — the lower the resistance, the better it conducts.
INSULATORS
Insulator substances do not conduct electricity. Insulators include gases, most ionic solids, most net-
work solids, almost all organic compounds, and all molecular and covalent liquids and solids.
METALLIC CONDUCTORS
A metallic conductor is an electronic conductor with a resistance that increases as temperature in-
creases. All metals are metallic conductors.
SEMICONDUCTORS
A semiconductor is an electronic conductor with a resistance that decreases as the temperature in-
creases. Semiconductor properties are a feature of metalloid elements such as silicon and germanium.
SUPERCONDUCTORS
A superconductor is an electronic conductor that conducts electricity with zero resistivity. Most su-
perconductors are metals (e.g., lead) or compounds cooled to near-absolute zero. A superconductor
substance has zero resistance below a certain temperature.
SEMICONDUCTING ELEMENTS
Semiconducting elements exhibit very low electrical conductivity at room temperature when pure; elec-
trical conductivity increases with temperature or with the addition of a certain element. The process of
adding small quantities of other elements to a semiconducting element to increase its conductivity is
called doping. See Figure B.1 for a schematic drawing of silicon semiconductor crystal layers.
N-TYPE SEMICONDUCTORS
In an n-type semiconductor, a minute amount of a group VA (15) element, such as arsenic (As), is
added to very pure silicon (Si). The As increases the number of electrons in the solid: Each Si atom
(Group IVA, 14) has four valence electrons, whereas each As atom has five. The additional electrons
317
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FIGURE B.1 Schematic drawing of silicon semiconductor crystal layers. (From World of Chemistry, 1st ed.,
by M.D. Joesten, D.O. Johnston, J.T. Netterville, J.L. Wood © 1990. Reprinted with permission of Brooks/Cole,
an imprint of the Wadsworth Group, a division of Thomson Learning. Fax 800 730-2215.)
enter the upper, normally empty conduction band of silicon and allow the solid to conduct. This type
of material is called an n-type semiconductor because it contains excess negatively charged electrons.
P-TYPE SEMICONDUCTORS
In a p-type semiconductor, Si (Group IVA, 14) is doped with an element from group IIIA (13), such
as boron (B). In this case, B has fewer valence electrons than Si, so the valence band is not completely
full. The band now has “holes.” Because the valence band is no longer full, it has turned into a con-
duction band and thus a current can flow. This type of material is called a p-type semiconductor be-
cause the absence of negatively charged electrons is equivalent to the presence of a positive charge.
TRANSISTORS AND OTHER ELECTRONIC DEVICES

TRANSISTORS
One of the most significant discoveries of the twentieth century was how electrical characteristics of
semiconductors can be modified by the controlled introduction of carefully selected impurities. This
led to the development of transistors, which have made possible all the electronic devices we now
take for granted, such as portable televisions, compact disc players, radios, calculators, and micro-
computers.
Various types of transistors (devices for controlling electrical signals) can be made by combin-
ing p- and n-type semiconductors. Transistors can be formed directly on the surface of a silicon chip,
which has made possible the microcircuits used in computers and calculators. Some of the latest
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Appendix B: Silicon Chips 319
computer chips contain microscopic electrical circuits integrated with as many as a million transis-
tors per centimeter of surface area.
CHIPS
The chip, a nickname for the integrated circuit, is a small slice of silicon that contains an intricate
pattern of electronic switches (transistors) joined by “wires” etched from a thin film of metal. Some
chips, known as memory chips, store information, while others combine memory with logic functions
to produce computer or microprocessor chips. Chip applications are almost infinite. A microproces-
sor chip, for example, can provide a machine with decision-making ability, memory for instructions,
and self-adjusting controls. In everyday life, we see many examples of chip applications: digital
watches; microwave oven controls; hand calculators; electronic cash registers for calculating total
bills, posting sales, and updating inventories; and computers in a variety of sizes and capacity.
SOLAR BATTERIES
The solar cell directly converts solar energy into electron flow. A silicon solar battery (also called a
solar cell) is composed of a silicon wafer doped with arsenic (an n-type semiconductor) over which
is placed a thin layer of silicon doped with boron (p-type semiconductor). The makeup of a silicon
solar battery is illustrated in Figure B.1.
In the absence of light, equilibrium exists between electrons and holes at the interface between
the two layers, which is called a p–n junction. Some electrons from the n-type layer diffuse into the
holes in the p-layer and are trapped. This leaves some positive holes in the n-layer. Equilibrium is
achieved when the positive holes in the n-layer prevent further movement of electrons into the p-
layer. When light falls on the surface of the cell, the equilibrium is upset. Energy is absorbed, which
permits electrons that were trapped in the p-layer to return to the n-layer. As electrons move across
the p–n junction into the n-layer through the wire, they pass through the electrical circuit and enter
the p-layer. Thus, an electric current flows when light falls on the cell and the external circuit is com-
pleted. The electric current can be used to run a motor or charge a battery, among many other tasks.
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Appendix C: Lasers
A laser is a source of an intense, highly directed beam of monochromatic light. The word “laser” is
an acronym for light amplification by stimulated emission of radiation. In a laser, electrons are raised
to a higher energy state by the absorption of energy in one form or another. If conditions are right,
the number of excited atoms exceeds the number in the ground state, and a population inversion ex-
ists. Not all substances can function as lasers. The laser process begins when one excited atom emits
a photon, which strikes another excited atom that is stimulated to emit a photon. These emissions
initiate further emissions and so on, until a cascade of photons is produced. In this way, the intensity
of the original one-photon emission is amplified enormously.
Lasers can be solid, liquid, or gas devices. Population inversion is achieved by optical pumping
with flashlights or with other lasers. It can also be achieved by such methods as chemical reactions
and discharges in gases.
RUBY LASERS
The ruby laser was one of the earliest. A very bright flashlight, similar to the kind used in the elec-
tronic flash in the modern camera, wraps around a ruby rod and provides the energy to pump the laser
into an excited state. The laser beam then emerges from the ruby through the partially reflecting end
as seen in Figure C.1. Ruby is comprised of aluminum oxide containing a small concentration of
chromium (III) ions (Cr3+) in place of some aluminum ions. The electron transitions in a ruby laser
are those of Cr+3 ions in solid Al2O3. Most of the Cr3+ ions are initially in the lowest energy level (level
1). If you shine light of wavelength 545 nm on a ruby crystal, the light is absorbed and Cr3+ ions un-
dergo transitions from level 1 to level 3. A few of these ions in level 3 emit photons and return to level
1, but most of them undergo radiationless transitions to level 2. In these transitions, the ions lose en-
ergy as heat to the ruby crystal, rather than emit photons. However, this spontaneous emission of Cr3+
is relatively slow. If you flash a ruby rod with a bright light at 545 nm, most of the Cr3+ ions end up
in level 2 for perhaps a fraction of a millisecond. This buildup of many excited species is crucial to
the operation of a laser. If these excited ions can be triggered to emit simultaneously, an intense emis-
sion will be obtained. The process of simultaneous emission is ideal for this triggering. When a pho-
ton corresponding to 694 nm encounters a Cr3+ ion in level 2, it stimulates the ion to undergo the tran-
sition from level 2 to level 1. The ion emits a photon corresponding to exactly the same wavelength
as the original photon. In the place of just one photon, there are now two photons, the original one
and the one obtained by stimulated emission. The net effect is to increase the intensity of the light at
this wavelength. Thus, a weak light at 694 nm can be amplified by stimulated emission of the excited
ruby. A sketch of the ruby laser is shown in Figure C.1.
GAS LASERS
One of the most powerful and efficient gas lasers uses CO2 mixed with He and N2. It produces laser
light with a wavelength in the infrared region of the spectrum.
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APPLICATIONS
The light from a laser has some unique properties. Laser light is coherent. This means that the waves
forming the beam are all in phase; that is, the waves’ maxima and minima occur at the same points
in space and time. The property of coherence of a laser beam is used in compact disc (CD) audio play-
ers.
Other properties of laser light are used in diverse applications. The ability of a laser to focus in-
tense light on a spot is used in the surgical correction of a detached retina in the eye. In effect, the
laser beam is used to “spot weld” on the retina.
The intensity of the laser beam is used in laser printers. These printers follow the principle of pho-
tocopiers but use a computer to direct the laser light in a pattern of dots to form an image.
In chemical research, laser beams provide intense monochromatic light to locate energy levels in
molecules, study the products of very fast chemical reactions, and analyze samples for small amounts
of particular substances.
FIGURE C.1 Ruby laser.

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Appendix D: Metals and Plants

Laszlo Gy. Szabo
Plants require several mineral substances. The uptake and assimilation of these substances are just as
important as those of carbon, hydrogen, oxygen, nitrogen, phosphorus, or sulfur. Because the role of
metals cannot be understood without an appreciation of the six “biogen” elements, they will also be
discussed indirectly in this short review.
Plants take up metals necessary for metabolism as well as several metals that are not necessary
(or at least the role of these metals in plant metabolism is not yet understood). These “unnecessary”
elements (mainly heavy metals) and excess quantities of micronutrients may not be absorbed; if ab-
sorbed, these substances are accumulated or excreted (and thus rarely cause toxic symptoms in
plants). However, plants are quite diverse in this respect; some taxa are sensitive to these unneces-
sary elements and others are tolerant.
Humans ingest toxic substances (e.g., lead or cadmium) in plant foods, both directly by eating
contaminated plants and indirectly by eating the products of animals fed contaminated plants. The
question of whether the toxic substance is found in plants (in the form of molecules within plant cells
or excreted and thus neutralized from a plant physiological point of view) or in dust on the surface
of the plant (epidermis, areoles, adsorbed to trichomes, etc.), is perhaps secondary.
Optimal concentrations of metals that are essential for plants depend on the plant genotype. The op-
timum amounts vary, not only by taxa but also by cultivar. Deficiency symptoms can often be recog-
nized via simple visual inspection, but chemical analysis is usually necessary for precise identification.
Adsorption of excessive quantities causes metabolic disorders. The relative proportions of certain met-
als must also be optimal. Nutritive disorders are characterized by changes in element composition, but
a significant and sometimes conspicuous change in element proportions may also occur in plants dam-
aged by pathogens or parasites. These changes can be measured especially well in the case of metals.
Much current research on plant physiology is focused on the synergy and antagonism of metals. Metals
in plant physiology are categorized according to relative quantities used by plants and effects on
plants.
Macronutrients (%, g/100 g): Potassium, calcium, and magnesium always taken up by plants
together with the nonmetal macronutrients nitrogen, phosphorus, and sulfur (usually in the
form of anions) (In the case of nitrogen fixing, bacteria have a significant role.)
Micronutrients (mg/g): Iron, manganese, zinc, copper, cobalt, molybdenum, selenium, sodium,
silicon (Chlorine is the only halogen considered to be essential for photosynthesis of higher
plants.)
Uncertain role: Vanadium, chromium, nickel, strontium, and aluminum
Mostly toxic: Arsenic, cadmium, and lead
MOST IMPORTANT METALS

The most important metals in plant physiology are briefly described below.
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POTASSIUM
Form of uptake: ion
Role: enzyme activation, photosynthesis, respiration, osmotic potential (especially the stomatal
opening mechanism), turgor, maintenance
Deficiency symptom: spotted lower leaves, necroses with browning, intercostal wilting, root
mucosity
CALCIUM
Form of uptake: ion
Role: cell membranes, enzyme activation (calmoduline), polysaccharide (Ca-pectate), inclu-
sion formation (Ca-oxalate, Ca-sulphate), gravitropism, cell-cycle control, senescence (cal-
cification)
Deficiency symptom: decay of apical buds, root mucosity
MAGNESIUM
Form of uptake: ion
Role: chlorophyll, ATP, cAMP, enzyme activation, DNA synthesis, RNA synthesis
Deficiency symptom: chlorosis, intercostal necrosis (midrib remaining green), root mucosity
IRON
Form of uptake: ion (II, III). Deficiency can be caused by excess phosphate, bicarbonate, Cu,
Zn, Co, Cd, Mn, or Ni. Chelate-forming siderophores (iminocarbonic acid polymers) bind
Fe(III), being reduced to Fe(II) in root tissue, which is transported and utilized in this form.
Role: chlorophyll synthesis, redox processes in photosynthesis and respiration (cytochromes,
Fe-S proteins, ferredoxin), nitrate and nitrogen reduction, cell division (phytopherritins)
Deficiency symptom: intercostal chlorosis in younger, then older leaves and later senescence
Accumulation: in older leaves
COPPER
Form of uptake: ion (I, II)
Role: redox processes, photosynthetic electron transport (plastocyanine), respiration (cyto-
chrome oxidase), metalloenzymes (e.g., aminooxidase, superoxide dismutases), nitrogen
fixation and nitrogen reduction, resistance to fungal diseases
Deficiency symptom: young leaves are dark green and spiraled, later necrosis
ZINC
Form of uptake: ion
Role: enzyme activation (e.g., peptidase, proteinase, phosphohydrolase, superoxide dismutase,
dehydrogenase, carboanhydrase), auxin biosynthesis, growth, seed formation
Deficiency symptom: small leaves, rosette formation, withering along leaf veins
MANGANESE
Form of uptake: ion
Role: chlorophyll biosynthesis, enzyme activation (e.g., pyruvate carboxylase, superoxide
dismutase)
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Appendix D: Metals and Plants 325
Deficiency symptom: uneven withering of young leaves, necroses (vein remaining green)
MOLYBDENUM
Form of uptake: molybdenate anion (II)
Role: nitrate reduction (nitrate reductase), nitrogen fixation (nitrogenase), chlorophyll biosyn-
thesis
Deficiency symptom: intercostal chlorosis in older leaves, wrapped leaf lamina
SELENIUM
Form of uptake: selenate anion (II)
Role: antioxidant systems (glutathione peroxidase). Se analogs of S-containing amino acids
(selenomethionine, selenocysteine) in nontolerant plants take part in enzyme synthesis,
thereby producing toxic symptoms. Tolerant plants are able to distinguish between Se and
S; the nonprotein-forming amino acids are stored in the vacuole and do not take part in me-
tabolism.
SODIUM
Form of uptake: ion
Role: osmotic substance in the form of NaCl may be important in low concentrations; toxic in
high concentrations, causing potassium loss and membrane depolarization and calcium loss
of plasmalemma
COBALT
Form of uptake: ion
Role: nitrogen fixation, growth of nitrogen-fixing plants
SILICON
Form of uptake: silicate anion (II), silicic acid
Role: incrustating in cell wall, strengthens (e.g., by forming polysaccharide esters with orto-
silicic acid and iso-polyacids)
ALUMINUM
Form of uptake: ion
Role: not clear, growth stimulator in tolerant plants
ARSENIC
Form of uptake: arsenite (III), arsenate (III) anion
Role: toxic. Arsenite is more phytotoxic than arsenate accumulating in roots and older leaves
(low concentrations of phosphate (III) remove arsenate or arsenite from soil particles, thus
increasing their uptake; in higher concentrations, however, the effect is the opposite, dis-
placing them from root surface)
CADMIUM
Form of uptake: ion
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Role: toxic, although being bound to phytochelatins disturbs enzyme activity if free; binding
to the living parts of root zone damages the root; growth inhibitor causing chlorosis in leaves
LEAD
Form of uptake: ion
Role: toxic; enzyme inhibitor that causes chlorosis and red necroses in leaves, roots blacken
The most important micronutrients are the redox metals (Fe and Cu), which have an indispensable
role in photosynthetic and mitochondrial electron transport as electron carriers (cytochromes, iron-
sulfur proteins, ferredoxin, and plastocyanin).
METALLOENZYMES
Metal-containing enzymes (metalloenzymes) are also essential in plants. A few examples are listed
below.
Zinc Metalloenzymes
Carbonic anhydrase (1 Zn)
Carboxypeptidase A (1 Zn)
Alcohol dehydrogenase (2 Zn or 4 Zn)
Superoxide dismutase (2 Zn + 2 Cu)
Manganese Metalloenzymes
Pyruvate carboxylase (3–4 Mn)
Superoxide dismutase (2 Mn)
Copper Metalloenzymes
Superoxide dismutase (2 Cu + 2 Zn)
Cytochrome oxidase (2 Cu + 2 hemes)
Amine oxidase (3 Cu)
Ascorbic acid oxidase (4 Cu)
Iron Metalloenzymes
NADH dehydrogenase (4 Fe)
Succinate dehydrogenase (8 Fe)
Aldehyde oxidase (8 Fe + 2 Mo)
Sulphite oxidase (2 hemes + 2 Mo)
Cytochrome oxidase (2 hemes + 2 Cu)
Iron is also present in cytochrome P-450, which is important in detoxification and hydroxylation.
METAL UPTAKE SYSTEMS

Metal uptake levels are also determined by the nutrient available in the smallest amount in the soil or
other nutritive medium (Liebig’s “law of minimum”). This fact must be taken into consideration
when preparing nutritive solutions and cultures with a fluid or solid medium, as well as in agricul-
tural practices (Salisbury and Ross, 1992; Lea and Leegood, 1993).
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Metals dissolved in water and available for uptake get into the vascular tissue system of the root
as ions or complexes via root hairs. The type of movement of substances dissolved in water can be
classified as short, medium length, or long distance.
Short-distance metal transport (similar to the transport of water and nonmetallic ions or small
molecules of monosaccharides and disaccharides) takes place via membranes at the intracellular
level. However, the volume increase of the plant cell is restricted by the cell wall, which ensures a
flexible but solid structure. Nonosmotic uptake of substances sized under approximately 10 nm
through the cell wall is possible; thus, the cell wall almost fulfills the role of a filter. Larger particles
can get only to the border of the plasmalemma; meanwhile, they are mostly adsorbed to the macro-
molecules of the cell wall. The cell wall consists mainly of more or less lignified cellulose and hemi-
cellulose macromolecules, but special fibrillar glycoproteins (extensine, expansine) ensure its flexi-
bility. The cell wall is relatively poor in enzymes; usually only hydrolases and anionic peroxidases
are found here. Substances getting through the plasmalemma, including metal ions, get into the inner
part of the cell (cytosol) via osmotic forces. The plasmalemma is basically a barrier consisting of a
semipermeable membrane. The negative water potential maintained by dissolved salts (mainly
cations and anions dissolved in water) includes the swelling of the cytoplasm, the character and in-
tensity of genotype-dependent biosynthesis change, cell metabolism, and the beginning or continu-
ity of growth or division. Transport of materials takes place through monolayer membranes (e.g.,
plasmalemma at the border of the cytoplasm, tonoplast inside the cell, and at the border of the vac-
uole) and bilayer membranes (e.g., in the case of chloroplast and mitochondrium). Controlled ion
transport through these membranes is possible with specific carrier proteins and channel proteins.
Thus, ion transport is controlled by the plasmalemma and the tonoplast, allowing evolution of the
membrane potential, function of the proton pump through the proton-transporting ATP-ases, and fi-
nally, ATP-synthesis connected to the proton gradient and electron transport. The proton pump reg-
ulates the chemical reaction of the cytosol, and its balance ensures cation antiport and anion symport
(Tanner and Caspari, 1996).
At a medium-length distance, ions move more easily via the apoplast than via the symplast (e.g.,
through plasmodesmata). Transfer cells can be found around vascular bundles, mediating material
flow from the cortex parenchyma toward the tracheas. Metals may form complexes with organic sub-
stances that came into being by a shorter or longer biosynthetic pathway. For example, the phosphate
ester (polyphosphate) of meso-inositol (cyclic alcohol) is able to bind a large amount of iron, cal-
cium, or other metal temporarily and thus store it for a period of intensive metabolism (e.g., germi-
nation). Another example is the most common plant pigment, anthocyanin, as a polyphenol. Sugar
molecules (polyphenol glycosides) forming polyethers (glycosides) with phenolic hydroxy groups
allow many types of chelate formation. Metallo-anthocyanins, for instance, remain quite stable; they
can prevent for a long period the quick transformation or decomposition of cell-protecting molecules
(recently freed radical scavengers) and pigment-coloring (insect attracting) molecules. Furthermore,
due to their strongly hydrophilic nature, they bind large quantities of water molecules (hydration),
making the water potential of the cell more negative, thereby increasing the stress-enduring ability
of cells or tissues (drought, frost, etc.).
Transport in the xylem (tracheas, tracheids) and in the phloem (sieve tubes and companion cells,
at the gymnosperms sieve cells and albuminous cells) is called long-distance transport. The compo-
sition of xylem and phloem sap is not the same. Generally, phloem sap is richer than xylem sap, not
only in sucrose and amino acids synthesized by the plant but to a smaller extent also in transported
metals. Transport of dissolved substances in the phloem can be observed even when water movement
is not detectable.
The flow of aqueous solutions in the sieve tube occurs through the pores of the cribrum via plas-
modesmata. The osmotic pressure of the sieve-tube sap depends on the amount of substances dis-
solved in it. A positive pressure gradient emerges in the phloem, ensuring material flow from the apex
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toward the base. Xylem and phloem transport occurs in the opposite direction in leaves, roots, and
stem, but in the same direction in fruits. The latter may be responsible for significant metal accumu-
lation in seeds and fruits.
METAL ACCUMULATION
Supplying micronutrients (essential metals) continues to be an important issue in plant cultivation.
For optimal dosage, the needs of the plant species (and the cultivar) must be known, as well as soil
composition and ecostability characteristics of the grown cultivar. The timing and method of mi-
cronutrient supply are also of great importance for plants. Leaf sprays are frequently applied, as aque-
ous solutions can be absorbed by leaf tissues, as well as through stomata and an epidermis that is thin-
ner than other parts of the plant. The optimum can be determined only by careful chemical analysis
of plant and soil, but the quality of irrigation water must also be taken into account.
Metal accumulation is of great interest, especially from the viewpoint of environment protection.
Ions with an inhibitory character (heavy metals, such as lead and cadmium) can be bound with
chelate-forming substances (e.g., EDTA). The chelate-forming substances in living organisms are
usually called metallothioneins. These detoxifying polypeptides are rich in sulfur (hence their name).
Metallothioneins consisting of approximately 60 amino acids have been detected in fungi and verte-
brate animals.
The form of accumulation in plants containing certain mineral substances in high amounts can-
not be easily determined. In general, high concentrations are found dissolved in the vacuoles or
bound to peptides in the cytoplasm. Characteristics of accumulation sites can only be determined by
special, selective extraction techniques and analytical separation methods. At present few data are
available that can be used for comparison, and competent conclusions are also rare (Tolgyesi, 1969)
reported on selected plant species in Hungary that accumulate extremely high amounts of metals.
Mean concentrations of selected metals by plant species reported by Tolgyesi are listed below(sam-
ple number in parentheses).
Calcium, g/kg
Althaea officinalis, 22.5 (5)
Cirsium canum, 20.4 (10)
Cornus sanguinea, 21.5 (10)
Echium vulgare, 20.2 (5)
Euonymus europaeus, 21.6 (9)
Fagus sylvatica, 35.0 (3)
Ononis hircina, 18.6 (9)
Onosma arenaria, 72.0 (1)
Salix caprea, 22.0 (2)
Urtica dioica, 31.8 (9)
Iron, mg/kg
Alnus glutinosa, 632 (5)
Calamintha clinopodium, 1130 (1)
Cirsium canum, 603 (10)
Eupatorium cannabinum, 440 (6)
Inula britannica, 495 (7)
Linaria vulgaris, 453 (11)
Matricaria recutita, 496 (8)
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Ononis hircina, 607 (9)

Pulmonaria officinalis, 436 (6)
Schoenoplectus tabernaemontani, 630 (6)
Tussilago farfara, 500 (6)
Viburnum lantana, 450 (4)
Manganese, mg/kg
Abies alba leaf, 2200 (5)
Alnus glutinosa leaf, 208 (5)
Bolboschoenus maritimus, 235 (5)
Carex elata, 257, (8)
Carex pilosa, 261 (6)
Carpinus betulus, 540 (12)
Castanea sativa leaf, 850 (4)
Fagus silvatica leaf, 434 (6)
Glyceria maxima, 206 (5)
Larix decidua leaf, 1050 (5)
Luzula albida, 830 (5)
Picea abies leaf, 295 (4)
Quercus cerris leaf, 612 (6)
Quercus petraea leaf, 564 (6)
Quercus pubescens leaf, 706 (3)
Quercus robur leaf, 354 (7)
Salix alba leaf, 200 (13)
Salix caprea leaf, 285 (3)
Vaccinium myrtillus, 930 (4)
Zinc, mg/kg
Aristolochia clematitis, 50 (13)
Carex pilosa, 49 (6)
Datura stramonium, 47 (5)
Lactuca serriola, 47 (9)
Lepidium draba, 64 (5)
Picea abies leaf, 66 (4)
Populus alba leaf, 105 (6)
Populus italica leaf, 101 (5)
Populus nigra leaf, 79 (5)
Salix alba leaf, 83 (13)
Salix caprea leaf, 100 (3)
Copper, mg/kg
Alnus glutinosa leaf, 14.0 (5)
Aristolochia clematitis, 24.4 (13)
Artemisia vulgaris, 17.0 (21)
Bidens tripartita, 24.2 (6)
Caltha palustris, 14.4 (6)
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Datura stramonium, 15.4 (5)

Erigeron canadensis, 15.0 (7)
Ononis hircina, 18.1 (9)
Papaver rhoeas, 20.9 (5)
Solanum dulcamara, 17.1 (5)
Solanum nigrum, 15.4 (4)
Symphytum officinale, 14.8 (13)
Taraxacum officinale, 14.6 (5)
High levels of accumulation are primarily characteristics of the inherited physiological/bio-

chemical habits of taxa. However, it must be emphasized that the element composition of character
species in a natural plant association may vary within specific ranges under diverse edaphic and eco-
logical conditions (Szabo et al., 1985).
On the basis of several studies, Tolgyesi (1969) confirmed that inorganic chemotaxonomy is jus-
tified because certain taxonomic categories can be characterized by a specific ability to accumulate
inorganic elements. For example, plants belonging to the Boraginaceae and Betulaceae families are
especially rich in Ca; Lamiaceae, in Fe; Fagaceae and Betulaceae, in Mn; Solanaceae, Laminaceae,
Boraginaceae, and Asteraceae, in Cu; and Salicaceae, in Zn.
The sensitivity of most nonaccumulating, nontolerant plant species indicates the toxicity of met-
als. Effects can manifest as membrane damage, inhibition of enzymes, induction of enzymes, defense
mechanisms against metal phytotoxicity, and interaction of metals with nucleic acids (Farago, 1994).
Metal inhibition is reported for many enzymes. The high affinity of metals for sulfhydryl groups
is suggested as one of the main mechanisms of enzyme inhibition, including metal inhibition of en-
zymes related to photosynthesis (δ-ALA-dehydratase, protochlorophyllide reductase); inhibition of
photosynthetic electron transport and photophosphorylation; photosynthetic carbon dioxide fixation;
carbonic anhydrase; and superoxide dismutase.
Besides irreversible biochemical changes, enzyme induction effects are also known. These sec-
ondary indirect effects of metals are considered to play an important role in the stress metabolism in-
duced by toxic metal concentrations. Peroxidase induction has been observed in leaves and roots of
various plant species after application of toxic amounts of cadmium, zinc, copper, nickel, and mer-
cury. Similarly, the activity of catalase, esterases, and superoxide dismutase also increases due to the
effect of heavy metals.
Recent studies of special metal-binding proteins that are synthesized because of the effect of
heavy-metal stress are of special importance. These chelate-forming proteins are called phy-
tochelatins. Grill et al. (1989) were the first to report that Acer platanoides react in a highly sensitive
but specific way to heavy metals. The trees were planted in the zinc-rich soil of a closed mine. These
plants synthesized the phytochelatin suitable for binding Zn, whereas in the absence of Zn, synthe-
sis did not even begin.
Thus, in plant cells chelate-forming proteins are produced via the inductive effect of heavy metal
ions. To a certain extent, binding the ions maintains the normal metabolism of the cell. Phytochelatins
can be derived from glutathione (glutamyl-cysteinyl-glycine). Glutathione added to the medium of
the root culture of Rubia tinctorum increased the amount of cadmium-induced phytochelatins
(Kubota et al., 1995). Synthesis is catalyzed by the phytochelatin synthase (a special glutamylcys-
teine dipeptidyl-transpeptidase), a 2–11 dipeptide unit binding to glycine. Homophytochelatins with
a similar structure can also be detected, such as peptides containing alanine instead of glycine or the
so-called desglycyl peptides containing no glycine. The synthesis of one of the listed phytochelatins
is induced by Zn, Cd, Pb, Hg, Sb, Ni, Cu, Ag, Au, Bi, Te, and W.
Certain species can be used as bioindicators in determining the degree of heavy metal accumula-
tion and corresponding phenotypical changes. For instance, algae and mosses can usually accumulate
L1572_AppD 5/23/02 2:04 PM Page 331
higher amounts of heavy metals than vascular plants (e.g., Chlorella enriches Cd, Pb, Hg, Ag, Cu,
and Zn, and it can be utilized in industrial sewage purification). Certain moss species concentrate Zn,
Cu, Ni, Cd, and Cr without selectivity (1000–10,000 mg/kg), such as the so-called copper moss
(Gymnocolea acutiloba) living in Cu-containing soil or base rock. Heavy metal excretion may take
place through the cell wall, such as Pb and Zn excreted by Dicranella varia during the summer
drought, which appears as a dust layer on the moss carpet (amounts may reach 40,000–60,000
mg/kg). Some mosses concentrate radionuclids as well. For instance, Pleurozium schreiberi was able
to bind almost the full amount of nuclear fission products originating from an experimental nuclear
explosion. Mosses are also important in the circulation and accumulation of the radioactive isotope
Cs-137.
These examples also indicate that vascular plants accumulate much less heavy metal in the free
(ionic) state. Generally, they are temporarily dissolved in water via apoplast flow in vascular bundles
or adsorbed to other tissue elements. For instance, the leaves and cortex of spruce, pine, locust, and
poplar trees can accumulate 1 to 100 mg/kg of heavy metals. These “resistant” or “tolerant” plants
are suitable for measuring environment pollution as accumulation indicators. Among the herbaceous
plants, an example is the invasive Solidago canadensis, which, when located next to motorways, is
able to accumulate lead at a level of more than 100 mg/kg.
Balazsy (2000) draws attention to new considerations. Ambrosia artemisiifolia is widespread in
Europe and its pollen causes allergic reactions. This plant accumulates heavy metals to such a degree
at refuse dumps polluted with high levels of heavy metals that a significant amount of chromium,
copper, and zinc can be found even in its pollen. According to most available data, the zinc content
of the pollen is more significant than that of the vegetative organs of the plant. In certain cases, con-
centrations in pollen may reach 400 mg/kg of heavy metals when transferred long distances. In ad-
dition, by the mediation of pollen, this plant may be increasing the pollution of ecological systems,
and high concentrations of heavy metals in pollen are exacerbating allergy symptoms.
CONCLUSION
The relationship between metals and plants is very complicated. Several metals bound to enzymes
and vitamins are essential in the life of plants. Others are responsible for photosynthetic and mito-
chondrial electron transport by redox processes or take part in oxidative and reductive biochemical
reactions. Excess metals, especially heavy metals, are toxic to the plant but frequently, when they are
bound to special proteins, do not cause any damage. Knowing the amount of metals in plants is of
great importance in agriculture, food distribution and preparation, and environment protection. Exact
data and correct conclusions can be provided only through the application of chemical analytical
methods.
REFERENCES
Balazsy, S., Dissemination of Metals in the Ecological Systems, Bessenyei Press, Nyiregyhaza, Hungary, 2000.
Farago, M.E., Plants and the Chemical Elements, VCH, Weinheim, Germany, 1994.
Grill, E. et al., Phytochelatins, the heavy-metal-binding petides in plants, are synthesized from glutathione by a
specific glutamylcysteine dipeptidyl transpeptidase (polychelatin synthase), Proc. Natl. Acad. Sci.
U.S.A., 86, 6838–6842, 1989.
Kubota, H. et al., Phytochelatins (class III metallothioneins) and their desglycol peptides induced by cadmium
in normal root culture of Rubia tinctorum L., Plant Science, 106, 157–166, 1995.
Lea, P.J. and Leegood, R.C., Plant Biochemistry and Molecular Biology, John Wiley & Sons, Chichester,
England, 1993.
Salisbury, F.B. and Ross, C.W., Plant Physiology, Wadsworth, Belmont, CA, 1992.
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Szabo, L., Kevey, B., and Tolgyesi, Gy., Macroelement and microelement accumulation in the plant species of
hornbeam-oak communities living on different parent material in the Mecsek mountains. Bot. Kozlem.,
72, 1–2, 77–88, 1985.
Tanner, W. and Caspari, T., Membrane transport carriers, Annu. Rev. Plant Physiol. Plant Mol. Biol. 47,
595–626, 1996.
Tolgyesi, Gy., Microelement Content of Plants and Agricultural Aspects of THIS, Mezogazd, Kiado, Budapest,
1969.
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Appendix E: Toxicity of Cyanide

The cyanide ion (CN–) is the toxic agent in cyanide salts, such as sodium cyanide used in electro-
plating. Because cyanide is a relatively strong base, it reacts easily with many acids to form volatile
hydrogen cyanide (HCN). HCN boils at a relatively low temperature (26°C) and thus is a gas at tem-
peratures slightly above room temperature.
Cyanide is often used as a fumigant in storage facilities and cargo transport (e.g., ship holds) be-
cause it is toxic to most forms of life and, in gaseous form, can penetrate tiny openings, even insect
eggs. The cyanide ion is one of the most rapidly working poisons; lethal doses taken orally act in min-
utes. Cyanide poisons via asphyxiation, as does carbon monoxide (CO), but the mechanism of
cyanide poisoning is different. Instead of preventing the cells from getting oxygen, cyanide interferes
with oxidative enzymes, such as cytochrome oxidase. Oxidases — enzymes containing a metal, usu-
ally iron or copper — catalyze oxidation:
Metabolite (H)2 + 1/2 O2 → oxidized substance + H2O + E
The iron atom in cytochrome oxidase is oxidized from Fe2+ to Fe3+ to provide electrons for the re-
duction of O2. The iron regains electrons from other steps in the process. The cyanide ion forms sta-
ble cyanide complexes with metal ions of the oxidase and renders the enzyme incapable of reducing
oxygen or oxidizing the metabolite.
Cytochrome oxidase (Fe) + CN → Cytochrome oxidase (Fe) . . . CN → complex
In essence, the electrons of the iron ion are “frozen”; they cannot participate in the oxidation-re-
duction process. Plenty of oxygen gets to the cells, but the mechanism by which the oxygen is used
comes to a halt. Hence, the cell dies, and if this process occurs rapidly enough in vital organs, the vic-
tim dies. The mechanism of cyanide poisoning is illustrated in Figure E.1.
FIGURE E.1 Cyanide poisoning.
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L1572_AppF 5/23/02 2:05 PM Page 335
Appendix F: Components of
Nucleic Acid
Each cell in living organisms contains thousands of protein molecules. All of these molecules are
made up of the same 20 amino acids, but in numerous different sequences. Each species has a dif-
ferent set of protein molecules. Protein molecules also vary among individuals within a species, but
the range of variation is much less than that among species. Once scientists understood this, the next
question was how do the cells know which proteins to synthesize out of the extremely large number
of possible amino acid sequences? The answer to this question is heredity; that is, an individual gets
such information from the parents.
Since the late nineteenth century, biologists suspected that the transmission of hereditary infor-
mation from one generation to the next takes place in the nucleus of the cell, and the structure within
the nucleus, called chromosomes, has something to do with heredity. The information that determines
external characteristics (hair color, eye color, etc.) and internal characteristics (blood group, heredi-
tary diseases, etc.) resides in genes located inside the chromosomes. A gene can be defined as a seg-
ment of DNA (a segment of nucleotide in DNA) that codes for a functional product.
NUCLEIC ACIDS
Chemical analysis of nuclei showed that they are largely made up of special basic proteins and a type
of compound called nucleic acids. Nucleic acids are exceedingly large organic molecules containing
carbon, hydrogen, nitrogen, and phosphorus.
Nucleic acids are found in all living cells, with the exception of the red blood cells of mammals.
There are two kind of nucleic acids found in cells, each with a specific role in the transmission of
hereditary information. The two types are ribonucleic acid (RNA) and deoxyribonucleic acid (DNA).
DNA resides in the chromosomes of the nucleus. RNA is not found in the chromosomes, but rather
is located elsewhere in the nucleus and even outside the nucleus, in the cytoplasm. The building
blocks of nucleic acid chains are nucleotides. Nucleotides are composed of three simpler units: a
base, a sugar, and phosphorus. Nucleic acids are found in all living cells, with the exception of the
red blood cells of mammals.
DEOXYRIBONUCLEIC ACID (DNA)

A molecule of DNA is a chain of many nucleotide units. Each DNA nucleotide is comprised of a ni-
trogen-containing base, deoxyribose (pentose sugar), and a phosphate group (phosphoric acid mole-
cule). The nitrogen-containing base is adenine (A), guanine (G), cytosine (C), or thymine (T). All the
nitrogen-containing bases are ring structures containing atoms of carbon, hydrogen, oxygen, and ni-
trogen. Adenine and guanine are double-ring structures, collectively known as purines. Thymine and
cytosine are smaller, single-ring structures, called pyrimidines. Nucleotides are named according to
their nitrogenous base. Thus, a nucleotide containing thymine is called a thymine nucleotide, a nu-
cleotide containing adenine is called an adenine nucleotide, and so on. The term nucleoside refers to
the combination of a purine or pyrimidine plus a pentose sugar; it does not contain a phosphate group.
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Although the chemical composition of the DNA molecule was known before 1900, it was not
until 1953 that the organization of the chemical subunits was modeled by James Watson and Francis
Crick. Structural characteristics of this model of DNA molecules are summarized below:
1 The molecule consists of two strands with crossbars. The strands twist around each other
in the form of a double helix, so that the shape resembles a twisted ladder.
2. The uprights of the DNA ladder, called the backbone, consist of alternating phosphate
groups and the deoxyribose (sugar) portions of the nucleotide.
3. The rungs of the ladder contain nitrogenous bases in pairs joined by hydrogen bonds. As
shown in Figure F.1, a purine always pairs with a pyrimidine; that is, adenine always pairs
with thymine, and cytosine always pairs with guanine.
As discussed previously, cells contain hereditary material called genes, each of which is a seg-
ment of a DNA molecule. Genes determine all hereditary traits, and they control all activities that take
place within cells. When a cell divides, its hereditary information is passed on to the next generation.
This transfer of information is possible because of DNA’s unique structure.
Crick (b. 1916) and Watson (b. 1928), working in the Cavendish Laboratory at Cambridge, built
scale models of the double helical structure of DNA based on x-ray data from Rosalind Franklin
(1920–1958) and Maurice H.F. Wilkins (b. 1916). Knowing distances and angles between atoms, they
compared the task to solving a three-dimensional jigsaw puzzle. Watson, Crick, and Wilkins received
the Nobel Prize in 1962 for their work relating to the structure of DNA.
RIBONUCLEIC ACID (RNA)

The second principal kind of nucleic acid, RNA differs from DNA in several respects. Whereas DNA
is double stranded, RNA is usually single stranded. The five-carbon sugar in the RNA nucleotide is
ribose, which has one more oxygen atom than deoxyribose, and one of RNA’s bases is uracil, instead
of thymine. At least three different kinds of RNA have been identified in cells, known as messenger
RNA, ribosomal RNA, and transfer RNA. Each type of RNA has a specific role in cells.
L1572_AppF 5/23/02 2:05 PM Page 337
Appendix F: Components of Nucleic Acids 337
FIGURE F.1 Structure of DNA.

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Appendix G: Polarized Light

POLAR AND NONPOLAR COMPOUNDS
All diatomic molecules composed of atoms of various elements are polar (e.g., NaCl). In a mole-
cule, a dipole moment occurs when the charge in the chemical bonds is separated; that is, one part
of the molecule has a positive charge and the other a negative charge (e.g., water, H+OH–). All di-
atomic molecules built from the same atoms are nonpolar (e.g., Cl2). Nonpolar molecules have no
dipole moment. Examples of nonpolar compounds are methane and hexane.
POLARIZATION
Polarization is the process of confining the vibrations of the electric vector, constituting a transverse
wave in one direction. In unpolarized radiation, the vector oscillates in all directions perpendicular
to the direction of propagation.
POLARIZATION OF LIGHT
An ordinary light beam consists of waves vibrating in all possible planes perpendicular to its path.
If the light passes through some substance that permits only one of these components to pass
through, the waves in the resulting beam vibrate along the same plane. Such a light beam, described
as plane polarized, is illustrated in Figure G.1.
Plane Polarized Light

After reflection or transmission through certain substances (see Polaroid section below), the elec-
tric field is confined to one direction and the radiation is referred to as plane polarized light. The
plane can be rotated when it passes through certain substances.
Circular Polarized Light

In circular polarized light, the tip of the electric vector describes a circular helix about the direction of
propagation with a frequency equal to that of the light. The magnitude of the vector remains constant.
Elliptical Polarized Light

In elliptical polarized light, the vector also rotates about the direction of propagation but the ampli-
tude changes; a projection of the vector on a plane at right angles to the direction of propagation de-
scribes an ellipse. Circular and elliptical polarized light are produced using a retardation plate.
POLAROID
In 1808, French physicist Etienne Malus discovered that light can be polarized. One convenient way
is to pass ordinary light through a device composed of Iceland spar (crystalline calcium carbonate)
called a Nicol prism (invented in 1828 by British physicist William Nicol). A more recently devel-
oped polarizing material is Polaroid, invented by an American, E.H. Land. It contains a crystalline
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FIGURE G.1 In contrast to ordinary light (a), which vibrates in all planes, polarized light (b) vibrates in only
one plane.
organic compound properly oriented and embedded in a transparent plastic. Sunglasses are often
made from Polaroid.
Polaroid is a doubly refracting material that plane polarizes unpolarized light passed through it.
It consists of a plastic sheet strained in a manner that makes it birefringent by aligning its molecules.
Sunglasses incorporating a Polaroid material absorb light that is vibrating horizontally — produced
by reflection from horizontal surfaces — and thus reduce glare.
POLAROGRAPHY
Polarography is an electrochemical-based analytical technique. A dropping mercury electrode is used
as the cathode along with a large nonpolarizable anode. The dropping mercury electrode consists of
a narrow tube through which mercury is slowly passed into a dilute solution of the solution, so as to
form small drops at the end of the tube, which fall away. In this way, the cathode has a small surface
area and can be kept clean. A variable potential is applied to the cell and a plot of current against po-
tential (polarogram) made. As each chemical species is reduced at the cathode (in order of electrode
potentials) a step-wise increase in current is obtained. The height of each step is proportional to the
concentration of the component. This technique is useful for detecting trace amounts of metals and
for investigating solvated complexes.
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Appendix H: Stock Metal

Solutions
Aluminum (Al)
Dissolve 1.000 g of aluminum metal in dilute HCl via gentle heating. Dilute to 1 liter with reagent-
grade water (1000 mg/l).
Antimony (Sb)
Carefully weigh 2.7426 g of antimony potassium tartrate (K(SbO)C4H4O6.1/2H2O), and dissolve in
reagent-grade water and dilute to 1 liter (1000 mg/l).
Arsenic (As)
Dissolve 1.320 g of arsenic trioxide (As2O3) in 100 ml of reagent-grade water containing 4 g of
NaOH. Acidify the solution with 20 ml of concentrated HNO3 and dilute to 1 liter with reagent-
grade water.
Barium (Ba)
Dissolve 1.7787 g of barium chloride (BaCl2.2H2O) in reagent-grade water and dilute to 1 liter
(1000 mg/l).
Beryllium (Be)
Dissolve 11.6586 g of beryllium sulfate (BeSO4) in reagent-grade water containing 2 ml of concen-
trated HNO3 and dilute to 1 liter (1000 mg/l).
Cadmium (Cd)
Dissolve 1.000 g of cadmium metal in 20 ml of 1:1 HNO3 and dilute to 1 liter with reagent-grade
water (1000 mg/l).
Calcium (Ca)
Suspend 2.500 g of CaCO3 (dried for 1 h at 180°C) in reagent-grade water and dissolve by adding a
minimum of dilute HCl. Dilute to 1 liter with reagent-grade water (1000 mg/l).
Chromium (Cr)
Dissolve 1.923 g of chromium trioxide (CrO3) in reagent-grade water, acidify with HNO3, and di-
lute to 1 liter (1000 mg/l).
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Chromium Hexavalent (Cr6+)

Dissolve 0.2829 g of pure dried potassium dichromate (K2Cr2O7) and dilute to 1000 ml with reagent-
grade water (1 ml = 100 µg Cr).
Cobalt (Co)
Dissolve 1.000 g of cobalt metal in 20 ml of 1:1 HNO3 and dilute to 1 liter with reagent-grade water,
or 4.307 g of cobaltous chloride (CoCl2.6H2O), and dissolve in reagent-grade water. Add 10 ml of
concentrated HNO3 and dilute to 1 liter with reagent-grade water (1000 mg/l).
Copper (Cu)
Dissolve 1.000 g of electrolytic copper in 5 ml of HNO3 and dilute to 1 liter with reagent-grade water
(1000 mg/l).
Iron (Fe)
Dissolve 1.000 g of analytical-grade iron wire in 10 ml of HNO3 and reagent-grade water, and dilute
to 1 liter (1000 mg/l).
Lead (Pb)
Dissolve 1.599 g of lead nitrate (Pb(NO3)2) in reagent-grade water, acidify with 10 ml of HNO3, and
dilute to 1 liter (1000 mg/l).
Magnesium (Mg)
Dissolve 1.000 g of Mg metal (analytical reagent grade) in 20 ml of 1:1 HNO3 and dilute to 1 liter
with reagent-grade water (1000 mg/l). Alternatively, dissolve 0.829 g of magnesium oxide (MgO) in
10 ml of concentrated HNO3, and dilute to 1 liter with reagent-grade water (500 mg/l).
Manganese (Mn)
Dissolve 1.000 g of metal (analytical reagent grade) in 10 ml of HNO3 and dilute to 1 liter with
reagent-grade water (1000 mg/l).
Mercury (Hg)
Dissolve 0.1354 g of mercuric chloride (HgCl2) in 75 ml of reagent-grade water. Add 10 ml of con-
centrated HNO3 and adjust the volume to 100 ml with reagent-grade water (1 ml = 1 mg Hg).
Molybdenum (Mo)
Dissolve 1.840 g of ammonium molybdate ((NH4)6Mo7O24.4H2O) in reagent-grade water and dilute to
1 liter (1000 mg/l).
Nickel (Ni)
Dissolve 1.000 g of nickel metal (analytical grade) or 4.953 g of nickel nitrate (Ni(NO3).6H2O) in 10
ml of concentrated HNO3, and dilute to 1 liter with reagent-grade water (1000 mg/l).
L1572_AppH 5/23/02 2:06 PM Page 343
Appendix H: Stock Metal Solutions 343
Osmium (Os)
Procure a certified aqueous standard from a supplier.
Potassium (K)
Dissolve 1.907 g of potassium chloride (KCl, dried at 110°C) and dilute to 1 liter with reagent-grade
water (1000 mg/l).
Selenium (Se)
Dissolve 0.3453 g of selenious acid with assay 94.4% H2SeO3 and dilute to 200 ml (1000 mg/l).
Silver (Ag)
Dissolve 0.7874 g of anhydrous silver nitrate (AgNO3) in reagent-grade water. Add 5 ml of concen-
trated HNO3 and bring to volume in a 500-ml volumetric flask with reagent-grade water (1000 mg/l).
Sodium (Na)
Dissolve 2.542 g of sodium chloride (NaCl) in reagent-grade water, acidify with 10 ml of HNO3, and
dilute to 1 liter with reagent-grade water (1000 mg/l).
Thallium (Tl)
Dissolve 1.303 g of thallium nitrate (TlNO3) in reagent-grade water, acidify with 10 ml concentrated
HNO3, and dilute to 1 liter with reagent-grade water (1000 mg/l).
Tin (Sn)
Dissolve 1.000 g of analytical-grade tin metal in 100 ml of concentrated HCl, and dilute to 1 liter
with reagent-grade water (1000 mg/l).
Vanadium (V)
Dissolve 1.7854 g of vanadium pentoxide (V2O5) in 10 ml of concentrated HNO3, and dilute to 1 liter
with reagent-grade water (1000 mg/l).
Zinc (Zn)
Dissolve 1.000 g of zinc metal in 10 ml of concentrated HNO3 and dilute to 1 liter with reagent-grade
water (1000 mg/l).
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Appendix I: Calculation for

Solid Matrices
MOISTURE DETERMINATION
Moisture in a solid is determined by drying a known quantity aliquot of the well-mixed sample at
103 to 105°C in a laboratory oven. After the dried sample is cooled in a desiccator, weigh and cal-
culate its percent moisture by using the following formula:
% moisture = [(g of solid – g of dried solid) × 100]/g of solid (I.1)
REPORTING OF RESULTS FOR SOLIDS

For solid matrices, the report is expressed as ppm (milligrams per kilogram) or ppb (micrograms per
kilogram). The report should state that the reported value is calculated on the wet base, sometimes
called as-is base, or on the dry base.
Wet base means that the original solid sample (soil, sediment, sludge, etc.) contains moisture;
therefore, the original weight of the sample incorporates the weight of the moisture. Consequently,
the weight of the sample is incorrect. When the moisture content of the sample is known, the ana-
lyst can make the necessary corrections. For this calculation, use the following formula:
mg/kg on wet base = [mg/l × final volume of the sample after treatment]/g sample (I.2)
Once the percent moisture of the sample is known, correct the error caused by the moisture content
by using the following formula:
mg/kg on dry base = mg/kg on wet base/decimal fraction of dry solid (I.3)
Assume that a 5-g soil sample was weighed and digested for lead (Pb) analysis. After the
preparatory process (digestion), the final volume of the “ready-for-analysis sample” was 100 ml.
The Pb content of the digestate was found to be 0.56 mg/l (0.56 mg per 1000 ml, or 0.056 mg/100
ml). The 100-ml digestate corresponds to the 5-g soil sample; therefore, the 5-g soil sample contains
0.056 mg Pb. How much Pb will be in a 1000-g (1-kg) sample?
A 1-kg sample will contain 200 times more Pb, or 200 × 0.056 = 11.2 mg. Thus, the result is
11.2 mg/Kg (ppm) Pb on wet base. To avoid lengthy calculations, use formula I.2:
mg/kg Pb on wet base = (0.56 × 100)/5 = 11.2 mg/kg
The moisture content by weight of the soil sample was 12%; therefore, the dry soil weight is 88%.
Using Formula I.3:
mg/mg Pb on dry base = 11.2/0.88 = 12.72 mg/kg
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L1572_AppJ 5/23/02 2:06 PM Page 347
Appendix J: Plasma
Energy can be obtained by combining light nuclei into a heavier nucleus by nuclear fusion. Such fusion
reactions have been observed in the laboratory by means of bombardment using particle accelerators.
FUSION
According to the “big bang” theory of the formation of the universe, 98% of all matter is comprised
of helium. The theory postulates that the universe began with an explosion in which matter was
formed out of energy, and, at the beginning only the lightest element, hydrogen, existed. Later, as
the universe expanded, stars were born when the hydrogen clouds collapsed under gravitational
forces. In the cores of these stars, hydrogen nuclei fused together and formed helium.
The transformation of hydrogen nuclei into helium nuclei liberates a large amount of energy in
the form of photons — the smallest units of electromagnetic radiation — largely in the following
way:
H21 + H31 → He42 + n10 + energy
This process, called fusion, is how the sun generates energy. The reactions occurring in the sun are
essentially the same as those in a hydrogen bomb.
Fusion is the combination of very light nuclei. When very light nuclei, such as hydrogen, he-
lium, and lithium are combined or fused to form an element of higher atomic number, energy is re-
leased consistent with the greater stability of the elements in this intermediate atomic number range.
This energy, which comes from a decrease in mass, is the source of the energy released by the sun
and by hydrogen bombs. Nuclear fusion consists of the combining of two or more small nuclei into
a larger one, and the corresponding release of energy.
Materials for fusion reactions are available in enormous quantities. Deuterium is a relatively
abundant isotope: Of 6500 atoms of hydrogen in seawater, for example, one is a deuterium atom.
Thus, the oceans are a potential source of fantastic amounts of deuterium. A single liter of seawater
has 1.000 × 1022 atoms of deuterium. A single cubic kilometer of seawater, then, would contain
enough deuterium atoms with the potential energy to equal the burning of 1300 billion barrels of
crude oil (the approximate total amount of crude oil originally present on the planet).
When a deuterium and a tritium nucleus are transformed into a helium nucleus and a neutron, a
large amount of energy is released. Where does this energy come from? The combined mass of the
nuclei of two hydrogen isotopes is greater than the combined mass of the helium nucleus plus that
of a neutron. When the deuterium and tritium nuclei are converted to helium and a neutron, the extra
mass is converted to energy. Based on Albert Einstein’s (1879–1955) work, the amount of energy
released upon the conversion of mass follows:
E = mc2
where
E = energy (J).
m = mass (kg).
c = 3.0 × 108 m/sec.
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This equations states that the mass (m) converted (in kilograms), multiplied by the square of the
velocity of light (c2 in m2/sec2), is equal to the energy (E) created (in joules).
For example, 1 g of matter completely converted to energy would produce 8.8 × 1013 J, which is
enough energy to boil 34 million liters of water initially at 20°C. In summary, a lot of energy can be
obtained from a little mass.
PLASMA
Fusion reactions occur rapidly only at temperatures of 100 million °C or more. At these high tem-
peratures, atoms do not exist as such; instead, a plasma forms that consists of unbound nuclei and
electrons. Plasma is a gaseous state composed of ions. In plasma, nuclei merge or combine. To
achieve these high temperatures, the fusion reaction of a hydrogen bomb is required.
L1572_AppK 5/23/02 2:06 PM Page 349
Appendix K: Soxhlet Extraction

A Soxhlet extractor (Figure K.1) can be used to extract solutes from solids. Any volatile solvent can
be used. The solvent is vaporized, and in the condensed phase dropped onto the solid substance
placed in a thimble. When the liquid level fills the body of the extractor, it automatically siphons
back into the flask. This process continues repeatedly.
PROCEDURE SETUP
1. Put the known-weight solid substance in the porous thimble and place it in the inner tube
of the Soxhlet extractor.
2. Fill the flask half full of the extracting solvent.
3. Assemble the unit.
4. Turn on the cooling water. Heat.
5. When the extraction is complete, turn off the heat and the cooling water.
6. Dismantle the apparatus, and pour the extraction solvent containing the solute into a
beaker. Isolate the extracted component by evaporating the solvent.
7. Determine the component and calculate its concentration according to the analytical
method used.
FIGURE K.1 Soxhlet extraction.
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Appendix L: SI Units and

Conversion Factors
Conversion to Metric Measures

Symbol When You Know Multiply by To Find Symbol
Length in inches 2.54 centimeters cm
ft feet 30.48 centimeters cm
yd yards 0.9 meters m
mi miles 1.6 kilometers km
Area in2 square inches 6.5 square centimeters cm2
ft2 square feet 0.09 square meters m2
yd2 square yards 0.8 square meters m2
mi2 square miles 2.6 square kilometers km2
acres 0.4 hectares ha
Mass (weight) oz ounces 28 grams g
lb pounds 0.45 kilograms kg
short tons (2000 lb) 0.9 tonnes t
Volume tsp teaspoons 5 milliliters mL
Tbsp tablespoons 15 milliliters mL
fl oz fluid ounces 30 milliliters mL
c cups 0.24 liters L
pt pints 0.47 liters L
qt quarts 0.95 liters L
gal gallons 3.8 liters L
ft3 cubic feet 0.03 cubic meters m3
yd3 cubic yards 0.76 cubic meters m3
Temp. °F Fahrenheit 5/9 (after sub- Celsium °C
°C = 5/9(°F – 32) temperature tracting 32) temperature
°F °F
32 98.6 212
–40 0 40 80 120 160 200
–40 –20 0 20 40 60 80 100

°C 37 °C
351
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Conversion from Metric Measures

Symbol When You Know Multiply By To Find Symbol
Length mm millimeters 0.04 inches in
cm centimeters 0.4 inches in
m meters 3.3 feet ft
m meters 1.1 yards yd
km kilometers 0.6 miles mi
Area cm2 square centimeters 0.16 square inches in2
m2 square meters 1.2 square yards yd2
km square kilometers 0.4 square miles mi2
ha hectares (10,000 m2) 2.5 acres
Mass (Weight) g grams 0.035 ounces oz
kg kilograms 2.2 pounds lb
t tonnes (1000 kg) 1.1 short tons
Volume mL milliliters 0.03 fluid ounces fl oz
L liters 2.1 pints pt
L liters 1.06 quarts qt
L liters 0.26 gallons gal
m3 cubic meters 35 cubic feet ft3
m3 cubic meters 1.3 cubic yards yd3
Temp. °C Celsium 9/5 (then Fahrenheit °F
°F = (9/5°C) + 32 temperature add 32) temperature
L1572__Refs 5/23/02 2:07 PM Page 353
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L1572 Index 5/24/02 1:50 PM Page 355
Index
A Alkali metals
cesium, 15, 46
Absorption filters, 90–91 definition of, 13
Acid digestion francium, 15
aqueous sample and extracts, 234–235 lithium, See Lithium
description of, 233 potassium, See Potassium
flame atomic absorption spectrometry, 234 properties of, 13
graphite furnace spectrometry, 234–235 rubidium, 15, 46
procedure, 233 sodium, See Sodium
quality control, 233 toxic effects of, 46
sediments, 237–238 Alkaline earth metals
sludges, 237–238 barium, See Barium
soils, 237–238 beryllium, See Beryllium
Acid-mine drainage water, 11 calcium, See Calcium
Actinides, 7, 30 color of, 16
Actinium, 30 description of, 15–16
Acute effects, 39 magnesium, See Magnesium
Agricultural runoff natural sources of, 16
metal poisoning from, 12 strontium, 17, 47
sampling of, 220–221 Alkaline spills, 307
Agriculturally used waters Alnico, 18
description of, 69, 71 Alumina, 18
sampling of, 220–221 Aluminum
trace elements in, 72 compounds, 18–19
Air–acetylene flame consumer uses of, 18
acetylene, 122–123 flame atomic absorption spectrometry of, 272–273
calculations, 124 food sources of, 47
description of, 106, 121 graphite furnace atomic absorption spectrometry of,
metal-free water, 122–123 273
operation, 123 plant uptake of, 325
reagents, 122–123 properties of, 18–19, 271–272
sample analysis, 124 toxicity of, 47–48
standardization, 124 Aluminum chloride, 18
Air pollutants Aluminum hydroxide, 18
ambient air quality standard, 76–77 Aluminum sulfate, 18–19
Clean Air Act Ambient air quality standard, 76–77
air quality regulations under, 76 Ames test, 42
criteria pollutants under, 74 Ammonium nitrate, 136
noncriteria pollutants under, 74 Ammonium pyrrolidine dithiocarbamate, 112, 286–287
noncriteria standards, 76 Analytical data
primary, 74 confidence interval, 267
secondary, 74 correctness of, 260
Air sampling, 224–225 documentation, 265–266
355
L1572 Index 5/24/02 1:50 PM Page 356
performance checks, 262–263 matrix, 113–114, 117

quality control checks, 260–263 spectral, 116–118
report format for, 267 measurement, 104
significant figures, 266 metals in solution analyzed using, 104
units for expressing, 266–267 principles of, 86
Anion, 7 safety considerations, 118
Anthocyanin, 327 sample collection and preparation, 118
Antimony spectrophotometer
flame atomic absorption spectrometry of, 273–274 automatic samplers, 109
graphite furnace atomic absorption spectrometry of, burner, 107
274 detector, 108
natural sources of, 273 double-beam, 109
properties of, 31 flames, 106
sample preparation for, 236 light source for, 105–106
toxic effects of, 57 maintenance of, 118–120
Arsenic monochromator system, 107–108
gaseous hydride atomic absorption analysis of, 275 nebulizer, 106
graphite furnace atomic absorption spectrometry of, optics, 107–108
235–236, 275–276 performance checks of, 119
hydride generation atomic absorption spectrometry readout system, 108
for, See Hydride single-beam, 109
generation atomic absorption spectrometry steps involved in, 104–105
plant uptake of, 325 terminology associated with
properties of, 31 calibration, 109–110
toxic effects of, 56–57, 274 concentration, 110
Ash content, 251 detection limit, 110
Atom(s) optimum concentration ranges, 110–112
Bohr model of, 83 sensitivity, 110
description of, 2, 83–84 Atomic absorption spectrum, 84
mass number, 4 Atomic emission spectrometry
number, 3 description of, 161
particles of, 3 history of, 161–162
stability of, 84 inductively coupled plasma
structure of, 3 advantages of, 88, 164–165
subatomic particles, 3 blanks, 174–175, 177
Atomic absorption, 103 calculations, 177–178
Atomic absorption spectrometry characteristics of, 162–166
chelation-extraction method, 112 detection limits, 163
description of, 84, 103–104 discharge, 165–166
flame, See Flame atomic absorption spectrometry emissions collection and detection, 168–169
flashbacks in, 118 instrumentation
graphite furnace, See Graphite furnace atomic accessories, 170
absorption spectrometry autosamplers, 170
hydride generation, 112–113 calibration of, 176
interference components of, 166
background absorption, 116–117 control of, 169
chemical, 114–115, 117 description of, 166
description of, 113 drains, 167, 170
ionization, 115, 117 maintenance of, 170–171
L1572 Index 5/24/02 1:50 PM Page 357
Index 357
nebulizers, 167, 170 flame atomic absorption spectrometry of, 276–277

operation of, 175–176 graphite furnace atomic absorption spectrometry of,
performance verification, 171–172, 191–192 277
pumps, 167 properties of, 18
quality control, 177 toxic effects of, 47, 276
radio-frequency generators, 168, 171 Beer's law, 85
setup of, 175–176 Berylliosis, 16, 47
signal processing, 169 Beryllium
spray chambers, 167 flame atomic absorption spectrometry of, 278
torches, 167 graphite furnace atomic absorption spectrometry of,
interferences 278
chemical, 173 industrial uses of, 277
description of, 172 properties of, 16
matrix, 177 toxicity of, 47, 277
nonspectral, 173 Biological tests, 270
physical, 173 Bismuth
spectral, 172, 178 analysis of, 279
performance characteristics, 163–165 properties of, 20, 279
plasma functions, 166 toxic effects of, 50
principles of, 162–163 Black body radiation, 136
procedure, 175–178 Blanks
quality control, 178 analytical data, 260–261
reagents, 174–175 calibration, 192
sample analysis, 176 equipment, 215
source of, 162 inductively coupled plasma atomic emission
wavelengths spectrometry, 174–175, 177
description of, 164 method, 192
dispersive device, 168 reagent, 192
plasmas, 161 trip, 215
principles of, 86 Bohr model, 83
Atomic emission spectrum, 84 Boron, 55–56
Atomic fluorescence spectrometry, 87 Bromine, 9
Atomic mass, 4 Bunsen, Robert, 79
Atomic number, 3
C
Atomic spectroscopy
absorption, See Atomic absorption spectrometry Cadmium
atomization process, 87 flame atomic absorption spectrometry of, 279
description of, 84, 103 graphite furnace atomic absorption spectrometry of,
qualitative analysis uses of, 87 279–280
techniques for, 86 plant uptake of, 325–326
Atomic spectrum, 84 properties of, 29
Atomic weight, 4 toxic effects of, 52, 279
Atomization sources, 87 Calcium
Automated samplers, 205–206 deficiency of, 32
ethylenediamine-tetraacetic acid analysis of
B
apparatus, 281
Background equivalent concentration, 171, 191 calculations, 283–285
Baritosis, 47 description of, 281
Barium materials, 281
L1572 Index 5/24/02 1:50 PM Page 358
procedure, 283–285 Chelation/extraction method, for hexavalent chromium

reagents, 281–284 description of, 286–287
flame atomic absorption spectrometry of, 280–281 procedure, 287–288
food sources of, 32 quality control, 288
human metabolism uses of, 32 verification, 288
industrial uses of, 17 Chemical(s)
minerals of, 17 spills of, 306–307
plant uptake of, 324, 328 storage of, 310
properties of, 17 Chemical burns, 305
recommended daily amounts of, 32 Chips, 319
therapeutic uses of, 17 Chromium
water sources of, 280 alloys, 22–23
Calcium fluoride, 95 color of, 23
Calibration flame atomic absorption spectrometry of, 285–286
acceptance criteria, 261 graphite furnace atomic absorption spectrometry of,
accepted, 188 286
atomic absorption spectrometry, 109–110 hexavalent
atomic absorption spectrophotometer, 189 chelation/extraction method for
calibration validation standard, 186 description of, 286–287
check solutions, 186–187 procedure, 287–288
continuing, 188 quality control, 288
continuing calibration standard, 186, 190 verification, 288
curves, 97–98 colorimetric method for, 288–289
hydride generation atomic absorption spectrometry, sample preparation of, 239–241
158–159 industrial uses of, 23, 285
inductively coupled plasma analyzer, 189 properties of, 22–23
inductively coupled plasma atomic emission Chronic effects, 39
spectrometry, 176 Clean Air Act
initial, 187–188 air quality regulations under, 76
molecular spectrophotometer, 97–100 criteria pollutants under, 74
procedure for, 188–189 noncriteria pollutants under, 74
standard solutions, 184–186 noncriteria standards, 76
standards, 189 Clean Water Act
stock solutions, 184 description of, 60, 68
terminology associated with, 189–190 goals of, 68
unacceptable, 261 National Pollutant Discharge Elimination System
Calibration verification standard, 190 permit, 69
Carbon monoxide, 40 objectives of, 68
Carcinogens, 43–44 point source defined under, 69
Cassiterite, 19 policies of, 68
Cation, 7 pollutants defined under, 68
CERCLA, See Comprehensive Environmental water quality standards, 69
Response, Compensation, and Liability Act Cobalt
Cerium oxide, 30 description of, 289
Cesium graphite furnace atomic absorption spectrometry of,
properties of, 15 290
toxicity of, 46 plant uptake of, 325
Cesium iodide, 95 properties of, 25
Chelates, 21, 45 Cobalt chloride test, 100
L1572 Index 5/24/02 1:50 PM Page 359
Index 359
Cobaltite, 25 Correlation coefficient, 98

Cold-vapor atomic absorption spectrometry Corrosive poisons, 40–41
advantages of, 143 Corrosivity, 72
apparatus, 144–145 Corundum, 18
calculations and reporting, 150 Cuvette, 89, 91
description of, 113, 143 CWA, See Clean Water Act
detection limit, 143 Cyanide
instrument operation, 147 description of, 40
interferences toxicity of, 333
certain volatile organic materials, 150
D
copper, 149
seawater, brines, and industrial effluents high in Data
chlorides, 150 analytical
sulfides, 149 confidence interval, 267
limitations of, 143 correctness of, 260
procedure, 145–147 documentation, 265–266
quality control requirements, 150 performance checks, 262–263
safety, 151 quality control checks, 260–263
sample report format for, 267
collection, preservation, and handling of, 145 significant figures, 266
liquid, 148 units for expressing, 266–267
semisolids, 149 raw
solids, 149 analyst responsibilities, 249–250
standardization, 147–148 concentration factor, 251
Colivasa, 222 description of, 249, 255
Combined gas law, 254 dilution factor, 251
Composite samples, 204 milliequivalents per liter conversions, 252
Compounds milligrams per liter conversions, 252
definition of, 1 molar volume, 253
metal, 11 out-of-control conditions, 263
Comprehensive Environmental Response, parts per million conversions, 252–253
Compensation, and Liability Act, 61 records of, 256–260
Compressed gases, 309–310 rounding of, 255
Concentration factor, 251 significant figures, 255
Continuing calibration standard, 97, 190 solids, See Solids
Continuous source background correction, 116 Deoxyribonucleic acid, 42, 335–337
Continuous spectrum, 82 Detection limit
Contract laboratory protocol, 271 description of, 110
Conversion factors, 351–352 instrument, 195–196
Copper method, 194–195
in drinking water, 66 Deuterium discharge lamp, 94
flame atomic absorption spectrometry of, 290 Diffraction grating, 90, 95
food sources of, 34 Digestion procedures
industrial exposure to, 34, 290 acid, See Acid digestion
metabolic uses of, 34 description of, 228
metalloenzymes, 326 dry ashing, 231
overdose, 34 microwave-assisted
plant uptake of, 324, 329–330 calculation, 232
properties of, 26 microwave unit requirements, 231–232
L1572 Index 5/24/02 1:50 PM Page 360
procedure, 232 Electron sea model, 9–10

quality control, 233 Electrons, 3
nitric acid, 229 Elements
nitric acid–hydrochloric acid, 229 atomic mass of, 4
nitric acid–perchloric acid, 230 atomic weight of, 4
nitric acid–perchloric acid–hydrofluoric acid, 231 definition of, 1
nitric acid–sulfuric acid, 230 names of, 1–2
Dilution factor, 251 periodic table of, 4–8
Dimethyl mercury, 30, 54 symbols, 1
Dissolved metals transition, 7
sample collection for, 208 Environmental law
sample pretreatment of, 227 description of, 59
Dolomite, 16 federal, 59
Doping, 10 regulatory programs
Double-beam spectrophotometer, 93–94 Clean Water Act, 60
Drinking water Comprehensive Environmental Response,
analysis methods and references, 269 Compensation, and Liability Act, 61
copper in, 66 Federal Insecticide, Fungicide, and Rodenticide
lead in, 20, 49, 66 Act, 61
National Secondary Drinking Water Regulations, 67 Resource Conservation and Recovery Act, 60
Safe Drinking Water Act Safe Drinking Water Act, 60
amendments to, 62 Toxic Substances Control Act, 60
arsenic, 66 state, 59
copper, 66 Environmental management systems
description of, 61–62 definition of, 77
fluoride studies, 62 ISO 14001 standard, 77
groundwater disinfection rule, 63 Environmental Protection Agency
inorganic chemicals, 63–64 analysis methods, 270–271
lead, 66 contract laboratory protocol, 271
maximum contaminant levels, 62 priority toxic pollutants, 69–71
maximum contaminant levels goals, 62 responsibilities of, 59
radionuclides, 67 statement of work, 271
regulations of, 62 Ethylenediamine-tetraacetic acid
sulfate, 66 calcium analysis using
surface water treatment rule, 63 apparatus, 281
synthetic organic chemicals, 63–64 calculations, 283–285
total coliform rule, 63 description of, 281
volatile organic compounds rule, 62–63 materials, 281
sampling of, 218 procedure, 283–285
standards for, 64–65 reagents, 281–284
Dry ashing, 231 description of, 45, 50
Duplicates, 215, 261–262 Excited state, 83
Extraction procedure
E
oily wastes, 244–246
EDTA, See Ethylenediamine-tetraacetic acid toxicity
Einstein, Albert, 82, 347 apparatus, 241–242
Electrical discharges, 87 description of, 241
Electrodeless discharge lamps, 106, 112 materials, 241–242
Electromagnetic radiation, 80–82 procedure, 242–244
L1572 Index 5/24/02 1:50 PM Page 361
Index 361
reagents, 242 molybdenum, 295

sample collection, preservation, and handling, nickel, 296
241 potassium, 296–297
silver, 299
F
sodium, 300
Federal Insecticide, Fungicide, and Rodenticide Act, 61 thallium, 300–301
Ferric iron, 24 tin, 301
Ferromagnetism, 21 vanadium, 302–303
Ferrous iron, 24 zinc, 303–304
Field notebook, 256 nitrous oxide–acetylene flame method
Field quality control apparatus, 124
duplicates, 215, 261–262 description of, 124
equipment blanks, 215 operation, 125–126
field spiked samples, 215 reagents, 125
sample collection, 214–216 standardization, 126
trip blanks, 215 principles of, 121
FIFRA, See Federal Insecticide, Fungicide, and sample preparation for, 126–12238
Rodenticide Act spectrophotometer, 126–128
Fire hazards, 307–308 Flame emission spectrometry, 87, 161–162
Flame atomic absorption, 162 Fluoride
Flame atomic absorption spectrometry in drinking water, 62
acid digestion of samples, 234 studies of, 62
advantages of, 88 Focusing optic, 168
air–acetylene flame method Fossil fuel combustion, metal poisoning from, 12
acetylene, 122–123 Fraunhofer lines, 79
calculations, 124 Frequency, 80
description of, 121 Fusion, 347–348
metal-free water, 122–123
G
operation, 123
reagents, 122–123 Gadolinium, 30
sample analysis, 124 Gallium
standardization, 124 properties of, 19
characteristics of, 112 toxic effects of, 48
concentration ranges, 122 Gallium arsenide, 31
conditions for, 128 Galvanizing, 24
instrument performance checks, 190–191 Gamma rays, 81
metal-specific analysis Gas
aluminum, 272–273 compressed, 309–310
antimony, 273–274 noble, 7
barium, 276–277 Gas chromatography–mass spectroscopy, 314
beryllium, 278 Gas lasers, 321
cadmium, 279 Gaseous-hydride atomic absorption analysis, 275
calcium, 280–281 Germanium, 56
chromium, 285–286 Gold, 27, 54
copper, 290 Grab samples, 204, 218
iron, 291 Graphite furnace atomic absorption spectrometry
lead, 292 advantages of, 88
magnesium, 293 apparatus
manganese, 294 atomizer, 130–131
L1572 Index 5/24/02 1:50 PM Page 362
burner, 130 preparation of, 238

graphite furnace, 130–131 selenium determination sample preparation,
hollow cathode lamps, 130 235–236
operation, 133 sensitivity of, 129
sample dispensers, 132 signal, 134
spectrophotometer, 130 stabilized temperature platform furnace, 130,
strip-chart recorder, 131 139–140
water supply, 132 Grease, 239
application of, 129 Ground state, 83
arsenic determination sample preparation, 235–236 Groundwater
characteristics of, 113 analysis methods and references, 270
description of, 87, 162 disinfection rule, 63
instrument sampling of, 216–218
calibration of, 134 Gypsum, 16, 17
performance checks, 190–191
H
interference
background absorption, 136–137 Hafnium, 28, 53
baseline offset correction, 139 Hardness, 9
description of, 129 Hazardous waste
emission, 136 analysis methods and references, 270
nonspectral, 137–139 description of, 73
spectral, 135 evaluative criteria for, 73–74
metals-specific analysis leaching of, 74
aluminum, 273 Resource Conservation and Recovery Act, 73
antimony, 274 safety concerns, 223–224
arsenic, 275–276 sampling of, 222–224
barium, 277 Heavy metals
beryllium, 278 description of, 31–32
cadmium, 279–280 toxicity of, 44
chromium, 286 Heisenberg’s uncertainty principle, 3
cobalt, 290 Hematite, 24
iron, 291 Heme, 32–33
lead, 292 Hemochromatosis, 33
manganese, 294 Hemoglobin, 32–33
molybdenum, 295 Hemosiderosis, 33
nickel, 296 Herschel, William, 79
selenium, 297–299 Hexavalent chromium
silver, 299–300 chelation/extraction method for
thallium, 301 description of, 286–287
tin, 302 procedure, 287–288
vanadium, 303 quality control, 288
zinc, 304 verification, 288
multi-step temperature program, 133–134 colorimetric method for, 288–289
performance check, 140–141 sample preparation of, 239–241
principles of, 129–130 Hollow cathode lamp, 105, 112
reagents, 132–133 Hydride generation atomic absorption spectrometry
samples advantage and disadvantages of, 153
acid digestion of, 234–235 apparatus
analysis of, 134–135 description of, 154
L1572 Index 5/24/02 1:50 PM Page 363
Index 363
setup of, 158 signal processing, 169

application of, 153–154 spray chambers, 167
arsenic determinations, 159 torches, 167
atomizer, 154 interferences
calibration standards, 158–159 chemical, 173
description of, 112–113 description of, 172
interferences, 157 matrix, 177
materials for, 154–157 nonspectral, 173
principles of, 153 physical, 173
procedure, 158–159 spectral, 172, 178
reagents, 155–157 performance characteristics, 163–165
samples, 158 plasma functions, 166
selenium determinations, 159 principles of, 162–163
solutions, 154–157 procedure, 175–178
Hypercalcemia, 17, 32 quality control, 178
Hyperkalemia, 14 reagents, 174–175
Hyperphosphatemia, 19, 48 sample analysis, 176
source of, 162
I
wavelengths
Ideal gas law, 254 description of, 164
Ignitability, 72 dispersive device, 168
Indium Inductively coupled plasma discharge, 165
properties of, 19 Inductively coupled plasma mass spectrometry
toxic effects of, 48 advantages of, 88
Inductively coupled plasma atomic emission description of, 88
spectrometry Industrial discharges, 12
advantages of, 88, 164–165 Industrial waste, 12
blanks, 174–175, 177 Infrared absorption spectrum, 81
calculations, 177–178 Infrared radiation, 81
characteristics of, 162–166 Infrared spectrophotometer
detection limits, 163 description of, 95
discharge, 165–166 detector, 96
emissions collection and detection, 168–169 light source for, 95
instrumentation maintenance of, 101
accessories, 170 monochromator system, 95
autosamplers, 170 performance check of, 101
calibration of, 176 readout, 96
components of, 166 sample cells, 95–96
control of, 169 samples, 96–97
description of, 166 Inorganic chemicals, 63–64
drains, 167, 170 Instrument detection limit, 195–196
maintenance of, 170–171 Insulators, 317
nebulizers, 167, 170 Interference filters, 91
operation of, 175–176 International Union of Pure and Applied Chemistry, 4
performance verification, 171–172, 191–192 Iridium, 29, 53
pumps, 167 Iron
quality control, 177 deficiency of, 34
radio-frequency generators, 168, 171 dietary, 33
setup of, 175–176 disorders associated with, 33
L1572 Index 5/24/02 1:50 PM Page 364
flame atomic absorption spectrometry of, 291 blood levels of, 49

food sources of, 33 in drinking water, 20, 49, 66
graphite furnace atomic absorption spectrometry of, flame atomic absorption spectrometry of, 292
291 graphite furnace atomic absorption spectrometry of,
hemoglobin composition of, 32–33 292
megadoses of, 33 metals that interact with, 50
metabolic uses of, 32–33 plant uptake of, 326
metalloenzymes, 326 properties of, 19–20
plant uptake of, 324, 328–329 toxicity of, 20, 49–50, 292
properties of, 24–25, 291 Lead oxide, 20
rust formation, 24–25 Lethal dose 50, See LD50
types of, 24 Lethal effects, 39
Irrigation water Lewisite, 56
description of, 69, 71 Light
trace elements in, 72 continuous spectrum, 82
ISO 14001 EMS standard, 77 dual nature of, 81–82
Isotopes, fractional abundance of, 314–315 historical studies of, 79–80
line spectrum, 83
K
polarized, 339
Kirchhoff, Gustav, 79 visible spectrum of, 81
Lime, 17
L
Limestone, 16
Laboratory Line spectrum, 83
body protection in, 306 Lithium
carelessness in, 308–309 analysis of, 293
chemical spills, 306–307 properties of, 13–14, 293
cleanliness in, 305 toxic effects of, 46
compressed gases, 309–310 Lithium fluoride, 95
eye protection in, 305 Lithium hydroxide, 14
falling objects in, 308 Lithium-6-deuteride, 14
fire hazards, 307–308 Lutetium, 30
inhalation of liquids and gases in, 306 L’vov platform, 138–139
safety rules for, 311–312
M
skin contact with chemicals, 305
stockroom safety, 310–311 Macronutrients, 323
Laboratory notebook, 256 Magnesium
Laboratory-pure water, 180–181, 183 consumer uses of, 16–17
Lakes, 67 description of, 293
Landfills, metal poisoning from, 12 discovery of, 16
Lanthanides, 7, 30, 53 flame atomic absorption spectrometry of, 293
Lanthanum, 30 plant uptake of, 324
Lasers properties of, 16–17
applications for, 322 seawater separation, 11
definition of, 321 Magnetite, 24
gas, 321 Manganese
ruby, 321–322 flame atomic absorption spectrometry of, 294
Lawrencium, 30 graphite furnace atomic absorption spectrometry of,
LD50, 40 294
Lead metalloenzymes, 326
L1572 Index 5/24/02 1:50 PM Page 365
Index 365
plant uptake of, 324–325, 329 continuing calibration standard, 186, 190
properties of, 23–24 inductively coupled plasma analyzer, 189
sources of, 23, 293 initial, 187–188
toxicity of, 23–24 procedure for, 188–189
Manganese nodules, 11 standard solutions, 184–186
Manganese psychosis, 23 standards, 189
Manganin, 23 stock solutions, 184
Mass number, 4 terminology associated with, 189–190
Mass spectroscopy, 313–315 chemicals, 180
Mass spectrum, 313 description of, 179
Matter field quality control in, 181–184
compounds, 1 glassware used in, 179–180
definition of, 1 laboratory control standard, 187
pure substances, 1 laboratory-pure water, 180–181
Maximum contaminant levels, 62 quality control
Memory chips, 319 accuracy, 196–197, 200–201
Menke’s disease, 34 charts, 198–202
Mercuric chloride, 30 detection limits, 194–196
Mercuric nitrate, 29 field, 181–184
Mercury laboratory checks, 192–194
properties of, 9, 29–30, 294 laboratory-pure water, 180–181, 183
sample preparation for, 236–237 practical quantitation limit, 196
spills of, 307 precision, 196–199
toxicity of, 29–30, 54–55 sample collection for
Metabolic poisons, 40 agricultural discharges, 220–221
Metal(s), See also specific metal air, 224–225
compounds, 11 automated samplers, 205–206
determination methods for, 272 composite samples, 204
group IIIA, 18–19 containers, 206–207
group IVA, 19–20 dissolved metals, 208
group VA, 20 domestic sludge, 221
hardness of, 9 drinking water, 218
history of, 11 field quality control, 214–216
malleability of, 9 field records of, 208–214
nonmetals vs., 10 fish tissues, 224
plant uptake of grab samples, 204
accumulations, 328–331 groundwater, 216–218
systems for, 326–328 hazardous waste, 222–224
properties of, 9 holding time, 208
seawater extraction of, 11 manual, 204
sources of, 11 preparations, 203–204
transport of, 327 preservation, 207
Metal analysis rules, 206
calibration soil, 221
accepted, 188 surface waters, 218–219
atomic absorption spectrophotometer, 189 suspended metals, 208
calibration validation standard, 186 total metals, 207
check solutions, 186–187 waste water, 219–220
continuing, 188 sample preparation
L1572 Index 5/24/02 1:50 PM Page 366
acid-extractable metals, 228 procedure, 232

antimony, 236 quality control, 233
digestion, See Digestion procedures Microwaves, 80–81
disposal of samples, 247 Milligrams per liter conversions, 252
dissolved metals, 227 Minerals, 13, 32
documentation during, 246 Molar volume, 253
filtration of sample, 227–228 Molecular absorption, 85
greases, 239 Molecular spectrophotometry
hexavalent chromium, 239–241 description of, 89
log sheet for, 247–248 molecular absorption and color, 89
mercury, 236–237 spectrophotometer
oils, 239 built-in microprocessor, 95
silver, 236 calibration of, 97–100
total metals, 227 components of, 89–93
waxes, 239 cuvettes, 91
Metal poisoning, See also specific metal definition of, 89
description of, 11 detector, 91–92
sources of double-beam, 93–94
agricultural runoff, 12 infrared, See Infrared spectrophotometer
fossil fuel combustion, 12 light source for, 89–90
industrial waste and discharge, 12 monochromator, 90–91
landfills, 12 photosensitive detector, 91–92
mining, 11–12 readout device, 92–93
ore processing, 11–12 sample holder for, 91
stormwater runoff, 12 single-beam, 92–93
wastewater, 12 ultraviolet/visible, See Ultraviolet/visible
Metal toxicity spectrophotometer
description of, 40, 44 visible, 94
heavy metals, 44 wavelength selector, 90–91
mechanisms of, 45–46 Molybdenum
Metallic conduction, 317 flame atomic absorption spectrometry of, 295
Metallic mercury, 55 graphite furnace atomic absorption spectrometry of,
Metalloenzymes, 326 295
Metalloids plant uptake of, 325
antimony, See Antimony properties of, 28, 294
arsenic, See Arsenic toxic effects of, 51–52
properties of, 10 Monel, 25
silicon, 31 Monochromator
toxicity of, 55–57 atomic absorption spectrophotometer, 107–108
Method detection limit, 194–195 description of, 90–91
Methyl isobutyl ketone, 112, 286 infrared spectrophotometer, 95
Methyl mercury, 30, 54 Monomethylarsinic acid, 56
Methylarsinic acid, 56 Mutagens, 42–43
mg/m3, 252 Mutation, 42
Microbiological tests, 270
N
Micronutrients, 323
Microwave-assisted digestion National Pollutant Discharge Elimination System
calculation, 232 permit, 69
microwave unit requirements, 231–232 National Secondary Drinking Water Regulations, 67
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Index 367
Nebulizer, atomic absorption spectrophotometer, Osmium, 29, 53

106 Out-of-control conditions, 263
Neodymium, 30
P
Neurotoxins, 41
Neutrons, 3 Palladium
Newton, Isaac, 79 properties of, 29
Nickel toxic effects of, 52
flame atomic absorption spectrometry of, 296 Paramagnetic, 21
graphite furnace atomic absorption spectrometry of, Parts per million, 252–253
296 Periodic table of elements, 4–8
properties of, 25–26 Photochemical smog, 74
toxic effects of, 51 Photoemissive tube, 92
Niobium, 28, 51 Photons, 81
Nitrate, 228 Phototubes, 91–92
Nitric acid digestion, 229 Planck, Max, 81
Nitric acid–hydrochloric acid digestion, 229 Plants
Nitric acid–perchloric acid digestion, 230 calcium uptake by, 328
Nitric acid–perchloric acid–hydrofluoric acid copper uptake by, 329–330
digestion, 231 description of, 323
Nitric acid–sulfuric acid digestion, 230 genotype of, 323
Nitrous oxide–acetylene flame iron uptake by, 328–329
apparatus, 124 manganese uptake by, 329
description of, 106, 124 metal uptake by, 323
operation, 125–126 uptake systems, 326–328
reagents, 125 zinc uptake by, 329
standardization, 126 Plasma, 348
Noble gases, 7 Platinum, 29, 54
Nonmetals Poisons
metals vs., 10 corrosive, 40–41
properties of, 9 metabolic, 40
Nucleic acids Polar compounds, 339
deoxyribonucleic acid, 42, 335–337 Polarized light, 339
description of, 42, 335 Polarography, 340
ribonucleic acid, 336 Polaroid, 339–340
Nucleosides, 335 Ponds, 67
Nutrients, 67 Potassium
consumer uses of, 14
O
description of, 296
Octet rule, 7 flame atomic absorption spectrometry of, 296–297
Oil, 239 metabolic uses of, 34–35
Oily wastes plant uptake of, 324
extraction procedure for, 244–246 properties of, 14–15
spills of, 307 Potassium bromide, 95
Olivine, 11 Potassium bromide pellet technique, 96
Optical filters, 90 Potassium dichromate, 287
Optimum concentration range, 189 Potassium permanganate, 23
Ore Practical quantitation limit, 196
definition of, 11, 13 Praseodymium, 30
metal poisoning from mining of, 11 Precision, 196–199
L1572 Index 5/24/02 1:50 PM Page 368
Precision control charts, 202 Relative standard deviation, 197

Priority toxic pollutants, 69–71 Resource Conservation and Recovery Act
Prism, 90 description of, 60
Protons, 3 hazardous waste, 73
Psoralens, 44 Rhodium
Pure substances, 1 properties of, 29
Pyrimidines, 335 toxic effects of, 52
Ribonucleic acid, 336
Q
Rivers, 67
Quality control Rock, 13
accuracy, 196–197, 200–201 Rubidium
charts, 198–202 properties of, 15
checks, 260 toxicity of, 46
detection limits, 194–196 Ruby, 18
documentation, 265 Ruby lasers, 321–322
field, 181–184, 214–216 Rust, 24
laboratory checks, 192–194 Ruthenium
laboratory-pure water, 180–181, 183 properties of, 29
practical quantitation limit, 196 toxic effects of, 52
precision, 196–199
S
R Safe Drinking Water Act
Radio waves, 80 amendments to, 62
Radiofrequency generator, 165 arsenic, 66
Radionuclides, 67 copper, 66
Raw data description of, 60, 61–62
analyst responsibilities, 249–250 fluoride studies, 62
concentration factor, 251 groundwater disinfection rule, 63
description of, 249, 255 inorganic chemicals, 63–64
dilution factor, 251 lead, 66
milliequivalents per liter conversions, 252 maximum contaminant levels, 62
milligrams per liter conversions, 252 radionuclides, 67
molar volume, 253 regulations of, 62
out-of-control conditions, 263 sulfate, 66
parts per million conversions, 252–253 surface water treatment rule, 63
records of, 256–260 synthetic organic chemicals, 63–64
rounding of, 255 total coliform rule, 63
significant figures, 255 volatile organic compounds rule, 62–63
solids Safflere, 44
ash content of, 251 Sample collection
calculations for, 251 agricultural discharges, 220–221
cold vapor atomic absorption spectrometry of, air, 224–225
149 automated samplers, 205–206
matrices, 252 composite samples, 204
moisture of, 251 containers, 206–207
percentage composition of, 252 dissolved metals, 208
RCRA, See Resource Conservation and Recovery Act domestic sludge, 221
Reactivity, 72 drinking water, 218
Relative percent difference, 197 field quality control, 214–216
L1572 Index 5/24/02 1:50 PM Page 369
Index 369
field records of, 208–214 N-type, 317–318

fish tissues, 224 P-type, 318
grab samples, 204 Semimetals, 10
groundwater, 216–218 SI units, 351–352
hazardous waste, 222–224 Significant figures
holding time, 208 analytical data, 266
manual, 204 raw data, 255
preparations, 203–204 Silica, 71–72
preservation, 207 Silicon
rules, 206 plant uptake of, 325
soil, 221 properties of, 31
surface waters, 218–219 Silicon chips, 317–319
suspended metals, 208 Silver
total metals, 207 description of, 299
waste water, 219–220 flame atomic absorption spectrometry of, 299
Sample preparation graphite furnace atomic absorption spectrometry of,
acid-extractable metals, 228 299–300
antimony, 236 properties of, 26–27
digestion, See Digestion procedures sample preparation for, 236
disposal of samples, 247 toxic effects of, 52
dissolved metals, 227 Single-beam spectrophotometer, 93
documentation during, 246 Sludge
filtration of sample, 227–228 acid digestion of, 237–238
greases, 239 sample collection of, 221
hexavalent chromium, 239–241 Sludges, analysis methods and references, 270
log sheet for, 247–248 Smaltite, 25
mercury, 236–237 Smog, 74
oils, 239 Soda ash, 14
silver, 236 Sodium
total metals, 227 consumer uses of, 14, 300
waxes, 239 flame atomic absorption spectrometry of, 300
Sanitary landfills, metal poisoning from, 12 metabolic uses of, 34
Sapphire, 18 plant uptake of, 325
Scandium properties of, 14
properties of, 22 recommended daily allowance of, 34
toxic effects of, 50 seawater separation, 11
SDWA, See Safe Drinking Water Act in water, 14
Sediments Sodium absorption ratio, 14
acid digestion of, 237–238 Sodium bicarbonate, 14
analysis methods and references, 270 Sodium chloride, 95
Selenic acid, 154 Sodium hypochlorite, 14
Selenium Sodium sulfate decahydrate, 14
description of, 297 Soil
graphite furnace atomic absorption spectrometry of, acid digestion of, 237–238
235–236, 297–299 analysis methods and references, 270
toxicity of, 297 sampling of, 221
Semiconducting elements, 317 Solar batteries, 319
Semiconductors Solids
definition of, 10, 317 ash content of, 251
L1572 Index 5/24/02 1:50 PM Page 370
calculations for, 251 Spikes

cold vapor atomic absorption spectrometry of, 149 matrix, 193
matrices, 252 reagent water, 193–194
moisture of, 251, 345 sample, 193
percentage composition of, 252 unacceptable values for, 262
results reporting for, 345 Spodumene, 13
Solvents Stabilized temperature platform furnace, 130, 139–140
spill of, 307 Standard deviation, 196–197
storage of, 310 Stellite, 25
Soxhlet extraction, 349 Stibium, 31
Spectrometry, See Atomic absorption spectrometry Stormwater runoff, metal poisoning from, 12
Spectrophotometer Streams, 67
atomic absorption spectrometry Strontium
automatic samplers, 109 properties of, 17
burner, 107 toxic effects of, 47
detector, 108 Sublethal effects, 39
double-beam, 109 Sulfate, 66
flames, 106 Sulfuric acid, 287
light source for, 105–106 Superconductors, 317
maintenance of, 118–120 Superfund, See Comprehensive Environmental
monochromator system, 107–108 Response, Compensation, and Liability Act
nebulizer, 106 Surface water
optics, 107–108 agriculturally used, 69, 71
performance checks of, 119 analysis methods and references, 269–270
readout system, 108 classification of, 68
single-beam, 109 Clean Water Act
double-beam, 93–94 description of, 60, 68
flame atomic absorption spectrometry, 126–128 goals of, 68
graphite furnace atomic absorption spectrometry, National Pollutant Discharge Elimination System
130 permit, 69
infrared objectives of, 68
description of, 95 point source defined under, 69
detector, 96 policies of, 68
light source for, 95 pollutants defined under, 68
maintenance of, 101 water quality standards, 69
monochromator system, 95 ecosystems classified as, 67
performance check of, 101 industrial, 71–72
readout, 96 sampling of, 218–219
sample cells, 95–96 standards for, 67–68
samples, 96–97 treatment rule, 63
single-beam, 93 Synthetic organic chemicals, 63–64
ultraviolet/visible
T
characteristics of, 94–95
maintenance of, 101 Tantalum, 28
performance check of, 100 Technetium, 28–29
visible, 94 Tellurium, 57
Spectrophotometers, mass, 313 Teratogens, 41–42
Spectroscopy, mass, 313–315 Tetraethyllead, 20
Sphalerite, 27 Thalidomide, 41–42
L1572 Index 5/24/02 1:50 PM Page 371
Index 371
Thallium cadmium, See Cadmium

dermal exposure, 48 chromium, See Chromium
flame atomic absorption spectrometry of, cobalt, See Cobalt
300–301 complexes, 45
graphite furnace atomic absorption spectrometry of, consumer uses of, 21–22
301 copper, See Copper
properties of, 19 gold, 27, 54
toxic effects of, 48–49 hafnium, 28, 53
Thermite reaction, 18 inner
Thorium, 55 actinides, 30
Thulium, 30 definition of, 20
Tin lanthanides, 7, 30, 53
consumer uses of, 19 iridium, 29, 53
description of, 301 iron, See Iron
flame atomic absorption spectrometry of, 301 manganese, See Manganese
graphite furnace atomic absorption spectrometry of, mercury, See Mercury
302 molybdenum, See Molybdenum
properties of, 19 multiple oxidation states, 21
toxic effects of, 49 nickel, 25–26, 51
Tin chloride, 19 niobium, 28
Tin oxide, 19 osmium, 29, 53
Titanium overview of, 20–22
properties of, 22 palladium, 29, 52
toxic effects of, 50 platinum, 29, 54
Titanium oxide, 22 properties of, 20–22
Titanium tetrachloride, 22 rhodium, 29, 52
Total coliform rule, 63 ruthenium, 29, 52
Total metals scandium, 22, 50
sample collection, 207 silver, See Silver
sample pretreatment of, 227 tantalum, 28
Toxic effects, 39 technetium, 28–29
Toxic pollutants, priority, 69–71 titanium, See Titanium
Toxic substances toxicity of, 50–55
carcinogens, 43–44 tungsten, 28, 53
corrosive poisons, 40–41 vanadium, See Vanadium
metabolic poisons, 40 yttrium, 27–28, 51
mutagens, 42–43 zinc, See Zinc
neurotoxins, 41 zirconium, 28, 51
teratogens, 41–42 TSCA, See Toxic Substances Control Act
Toxic Substances Control Act, 60 Tungsten, 28, 53
Toxicity Tungsten halogen lamp, 94
definition of, 73
U
description of, 39
terminology associated with, 39–40 Ultraviolet/visible spectrophotometer
Toxicity characteristic leachate procedure, 74–75 characteristics of, 94–95
Toxicytosis, 39 maintenance of, 101
Transistors, 318 performance check of, 100
Transition elements, 7 Unified atomic mass unit, 3
Transition metals Uranium, 55
L1572 Index 5/24/02 1:50 PM Page 372
V Wet base, 345

Wilson’s disease, 34
Valence, 7
Work sheets, 256–259
Vanadium
description of, 302 X
flame atomic absorption spectrometry of, 302–303
X-rays, 81
graphite furnace atomic absorption spectrometry of,
Xylem, 327
303
properties of, 22 Y
toxic effects of, 50–51
Yttrium
Vermilion, 29
properties of, 27–28
Visible spectrophotometer, 94
toxic effects of, 51
Vitamin B12, 25–26
Volatile organic compounds rule, 62–63 Z
Volatile solvent spills, 307
Zeeman background correction, 116–117
W Zinc
description of, 303
Waste
flame atomic absorption spectrometry of, 303–304
characterization of, 72–73
graphite furnace atomic absorption spectrometry of,
hazardous, See Hazardous waste
304
Waste water
metalloenzymes, 326
metal poisoning from, 12
plant uptake of, 324, 329
sampling of, 219–220
properties of, 27
Water, See Drinking water; Groundwater; Irrigation
Zinc chromate, 23
water; Surface water; Waste water
Zinc oxide, 27
Wavelength
Zinc sulfide, 27
by color, 82
Zirconium
definition of, 80
properties of, 28
Wax, sample preparation for, 239
toxic effects of, 51

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Environmental

Library of Congress Cataloging-in-Publication Data

TD196.M4 C78 2002

Visit the CRC Press Web site at www.crcpress.com

© 2002 by CRC Press LLC

No claim to original U.S. Government works

List of Figures and Tables

1.1 Typical atom.

1.1 Names and Symbols of Elements Derived from Latin Words

3.3 Selected Inorganic Chemicals Carcinogenic to Humans

Chapter 1 Introduction to Metals

Chapter 2 Discussion of Metallic Elements

Chapter 3 Toxicity of Metals

3.1.2 Toxic Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..39

Chapter 4 STANDARDS RELATED TO METALLIC POLLUTANTS

4.9 ISO 14001 and Environmental Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .77

Chapter 5 FUNDAMENTALS OF SPECTROSCOPY

Chapter 6 MOLECULAR SPECTROPHOTOMETRY

Chapter 7 ATOMIC ABSORPTION SPECTROMETRY

Chapter 8 DIRECT ASPIRATION OR FLAME ATOMIC

Chapter 9 GRAPHITE FURNACE ATOMIC

9.4 Interferences and the Graphite Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .135

Chapter 10 COLD-VAPOR ATOMIC ABSORPTION

Chapter 11 HYDRIDE-GENERATION ATOMIC

11.2 Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .153

Chapter 12 INDUCTIVELY COUPLED PLASMA ATOMIC

12.5.4 Mixed Calibration Standard Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .174

Chapter 13 QUALITY CONTROL IN METALS ANALYSIS

13.9 Detection Limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .194

Chapter 14 SAMPLE COLLECTION FOR METALS ANALYSIS

14.9.5 Sampling Agricultural Discharges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .220

Chapter 15 SAMPLE PREPARATION FOR METALS ANALYSIS

Chapter 16 CONVERTING RAW DATA INTO

Chapter 17 REPORTING ANALYTICAL DATA

Chapter 18 SELECTED METHODS FOR DETERMINATION

18.11.1 Chelation/Extraction Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .286

Chapter 19 Laboratory Safety Rules

1.1.2.1 Element Symbols

1.1.2.2 Element Names

2 Environmental Sampling and Analysis for Metals

God or Astronomical Body

1.1.3.1 Subatomic Particles

1.1.3.2 Atomic Number

Atomic number = number of protons (+) = number of electrons (–)

4 Environmental Sampling and Analysis for Metals

1.1.3.3 Mass Number

Mass number = number of protons + number of neutrons

1.1.3.4 Atomic Mass and Atomic Weight

1.2 PERIODIC TABLE OF ELEMENTS

6 Environmental Sampling and Analysis for Metals

Periodic Table of the Elements

The periodic table with group names is shown in Table 1.6.

Alkaline earth metals

Boron aluminum group

1.3 PROPERTIES OF METALS, NONMETALS, AND METALLOIDS

10 Environmental Sampling and Analysis for Metals

Positive ions from the metal

Electron cloud that

FIGURE 1.3 Electron sea model.

1.3.3 METALLOIDS OR SEMIMETALS

1.4 EARLY HISTORY OF METAL USE

1.5 SOURCES OF METALS AND THEIR COMPOUNDS

1.6 SOURCES OF METAL POLLUTION

12 Environmental Sampling and Analysis for Metals